U.S. patent number 10,767,047 [Application Number 16/104,028] was granted by the patent office on 2020-09-08 for reinforced polyamide molding compounds having low haze and molded bodies therefrom.
This patent grant is currently assigned to EMS-Patent AG. The grantee listed for this patent is EMS-PATENT AG. Invention is credited to Etienne Aepli, Heinz Hoff, Botho Hoffmann.
United States Patent |
10,767,047 |
Aepli , et al. |
September 8, 2020 |
Reinforced polyamide molding compounds having low haze and molded
bodies therefrom
Abstract
The present invention relates to a polyamide molding compound
comprising the following components or consisting of these
components: (A) 50 to 95 wt % of a mixture comprising the specific
polyamides (A1) and (A2); (B) 5 to 50 wt % of at least one glass
filler having a refractive index in the range from 1.510 to 1.539;
(C) 0 to 10 wt % of at least one additive; wherein the weight
proportions of the components (A) to (C) add up to 100% by weight;
wherein the content of (A1) in the mixture (A) is >50 wt %, if
the ratio is .DELTA.2/.DELTA.1>1 and the content of (A2) in the
mixture (A) is >50 wt %, if the ratio is
.DELTA.2/.DELTA.1.ltoreq.1, where .DELTA.1=n(A1)-n(B) applies and
.DELTA.2=n(B)-n(A2) applies; wherein the transparent polyamides
(A1) and (A2) have a transparency of at least 90% and a haze of at
most 3%; and wherein the mixture (A) has a transparency of at least
88% and a haze of at most 5%. The present invention furthermore
relates to molded bodies composed of these polyamide molding
compounds.
Inventors: |
Aepli; Etienne (Domat/Ems,
CH), Hoffmann; Botho (Domat/Ems, CH), Hoff;
Heinz (Tamins, CH) |
Applicant: |
Name |
City |
State |
Country |
Type |
EMS-PATENT AG |
Domat/Ems |
N/A |
CH |
|
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Assignee: |
EMS-Patent AG (Domat/Ems,
CH)
|
Family
ID: |
1000005041186 |
Appl.
No.: |
16/104,028 |
Filed: |
August 16, 2018 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20190055404 A1 |
Feb 21, 2019 |
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Foreign Application Priority Data
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Aug 18, 2017 [EP] |
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17186918 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G
69/36 (20130101); C08G 69/265 (20130101); B32B
27/34 (20130101); C08L 77/06 (20130101); C08L
77/06 (20130101); C08K 7/14 (20130101); C08L
77/06 (20130101); C08L 2201/10 (20130101) |
Current International
Class: |
C08L
77/06 (20060101); C08G 69/26 (20060101); C08G
69/36 (20060101); B32B 27/34 (20060101) |
Field of
Search: |
;524/492,538 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2 169 008 |
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Mar 2010 |
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EP |
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WO 2015/132510 |
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Sep 2015 |
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WO |
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Other References
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applicant.
|
Primary Examiner: Teskin; Fred M
Attorney, Agent or Firm: Leydig, Voit & Mayer, Ltd.
Claims
The invention claimed is:
1. A polyamide molding compound comprising the following
components: (A) 50 to 95 wt % of a mixture consisting of the
polyamides (A1) and (A2), wherein (A1) is at least one transparent,
semi-aromatic polyamide having at least 25 mol % of monomers having
aromatic structural units, related to the total quantity of
diamines and dicarboxylic acids in the polyamide (A1) that is
amorphous or microcrystalline; and (A2) is at least one transparent
polyamide having less than 25 mol % of monomers having aromatic
structural units, related to the total quantity of diamines and
dicarboxylic acids in the polyamide (A2) that is amorphous or
microcrystalline; (B) 5 to 50 wt % of at least one glass filler
having a refractive index in the range from 1.510 to 1.539; and (C)
0 to 10 wt % of at least one additive; wherein the weight
proportions of the components (A) to (C) add up to 100% by weight;
wherein the content of (A1) in the mixture (A) is >50 wt %, if
the ratio is .DELTA.2/.DELTA.1>1 and the content of (A2) in the
mixture (A) is >50 wt %, if the ratio is
.DELTA.2/.DELTA.1.ltoreq.1, where .DELTA.1=n (A1)-n(B) applies and
.DELTA.2=n(B)-n(A2) applies; n being the refractive index measured
according to ISO 489 (1999-04), wherein the transparent polyamides
(A1) and (A2) have a transparency of at least 90% and a haze of at
most 3%; and wherein the mixture (A) has a transparency of at least
88% and a haze of at most 5%.
2. The polyamide molding compound in accordance with claim 1,
wherein the polyamide mixture (A) comprises 51 to 95 wt % of
polyamide (A1) and 5 to 49 wt % of polyamide (A2) if
.DELTA.2/.DELTA.1>1; or the polyamide mixture (A) comprises 51
to 95 wt % of polyamide (A2) and 5 to 49 wt % of polyamide (A1) if
.DELTA.2/.DELTA.1.ltoreq.1; and/or the proportion of component (A)
in the polyamide molding compound is in the range from 55 to 90 wt
% with respect to the sum of components (A) to (C); and/or the
proportion of component (B) in the polyamide molding compound is in
the range from 10 to 40 wt % with respect to the sum of components
(A) to (C); and/or the proportion of component (C) in the molding
compound is in the range from 0 to 7 wt % with respect to the sum
of components (A) to (C).
3. The polyamide molding compound in accordance with claim 1,
wherein the transparent polyamides (A1) are made up of the
following monomers: (a-A1) 20 to 100 mol % of cycloaliphatic
diamines, with respect to the total quantity of diamines; (b-A1) 0
to 80 mol % of diamines having aromatic structural units, with
respect to the total quantity of diamines; (c-A1) 0 to 80 mol % of
open-chain cycloaliphatic diamines, with respect to the total
quantity of diamines; (d-A1) 0 to 75 mol % of open-chain aliphatic
dicarboxylic acids, with respect to the total quantity of
dicarboxylic acids; (e-A1) 25 to 100 mol % of aromatic dicarboxylic
acids, with respect to the total quantity of dicarboxylic acids;
(f-A1) 0 to 75 mol % of cycloaliphatic dicarboxylic acids, with
respect to the total quantity of dicarboxylic acids; and (g-A1) 0
to 40 wt % of lactams and/or aminocarboxylic acids having 6 to 12
carbon atoms, with respect to the total quantity of the monomers
(a-A1) to (g-A1), wherein the sum of the diamines (a-A1), (b-A1),
and (c-A1) produces 100 mol %; wherein the sum of the dicarboxylic
acids (d-A1), (e-A1), and (f-A1) produces 100 mol %; and wherein
the sum of the monomers (b-A1) and (e-A1) amounts to at least 25
mol %, with respect to the sum of the total diamines and of the
total dicarboxylic acids in the polyamide (A1).
4. The polyamide molding compound in accordance with claim 1,
wherein the transparent polyamide (A1) comprises at least 27 mol %,
and in the range from 25 to 100 mol % of monomers having aromatic
structural units, with respect to the total quantity of diamines
and dicarboxylic acids in the polyamide (A1).
5. The polyamide molding compound in accordance with claim 1,
wherein the transparent polyamides (A2) are made up of the
following monomers: (a-A2) 20 to 100 mol % of cycloaliphatic
diamines, with respect to the total quantity of diamines; (b-A2) 0
to less than 50 mol % of diamines having aromatic structural units,
with respect to the total quantity of diamines; (c-A2) 0 to 80 mol
% of open-chain aliphatic diamines, with respect to the total
quantity of diamines; (d-A2) 20 to 100 mol % of open-chain
aliphatic dicarboxylic acids, with respect to the total quantity of
dicarboxylic acids; (e-A2) 0 to less than 50 mol % of aromatic
dicarboxylic acids, with respect to the total quantity of
dicarboxylic acids; (f-A2) 0 to 80 mol % of cycloaliphatic
dicarboxylic acids, with respect to the total quantity of
dicarboxylic acids; and (g-A2) 0 to 40 wt % of lactams and/or
aminocarboxylic acids having 6 to 12 carbon atoms, with respect to
the total quantity of the monomers (a-A2) to (g-A2); wherein the
sum of the diamines (a-A2), (b-A2), and (c-A2) produces 100 mol %;
wherein the sum of the dicarboxylic acids (d-A2), (e-A2), and
(f-A2) produces 100 mol %; and wherein the sum of the monomers
(b-A2) and (e-A2) amounts to less than 25 mol %, with respect to
the sum of the total diamines and of the total dicarboxylic acids
in the polyamide (A2).
6. The polyamide molding compound in accordance with claim 1,
wherein the transparent polyamide (A2) comprises at most 23 mol %
of monomers having aromatic structural units, with respect to the
total quantity of diamines and dicarboxylic acids in the polyamide
(A2).
7. The polyamide molding compound in accordance with claim 1,
wherein the transparency measured in accordance with ASTM D1003 at
a molded body (plate with the dimensions 60.times.60.times.2 mm)
manufactured from the polyamide molding compound amounts to at
least 80%; and/or the haze measured in accordance with ASTM D1003
at a molded body (plate with the dimension 60.times.60.times.2 mm)
manufactured from the polyamide molding compound amounts to a
maximum of 40%; and/or the arithmetical mean roughness Ra
determined in accordance with DIN EN ISO 4287 (2010-07) at a molded
body (plate with the dimension 60.times.60.times.2 mm) produced
from the polyamide molding compound using a MarSurf XR1 Surface
Measuring Station amounts to at most 0.12 .mu.m, and/or has a
surface roughness R.sub.z of at most 1.50 .mu.m.
8. The polyamide molding compound in accordance with claim 3,
wherein the cycloaliphatic diamine (a-A1) is selected from the
group consisting of bis(4-amino-3-methylcyclohexyl)methane,
bis-(4-aminocylcohexyl)methane,
bis-(4-amino-3-ethylcyclohexyl)methane,
bis-(4-amino-3,5,-dimethylcyclohexyl)methane, 2,6-norbornane
diamine, 2,6-bis-(aminomethyl)-norbornane, 1,3-diaminocyclohexane,
1,4-diaminocyclohexanediamine, isophorone diamine,
1,3-bis-(aminomethyl)cyclohexane, 1,4-bis-(aminomethyl)cyclohexane,
2,2-(4,4'-diamonodicyclohexyl)propane, and mixtures thereof; and/or
the diamine having aromatic structural unit (b-A1) is a
xylylenediamine; and/or the open-chain aliphatic diamine (c-A1) is
a hexanediamine, and/or the aliphatic dicarboxylic acid (d-A1) is
selected from the group consisting of 1,6-apidic acid,
1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic
acid, 1,12 dedecanedioic acid, 1,13-tridecanedioic acid,
1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid,
1,18-octadecanedioic acid, and mixtures thereof; and/or the
aromatic dicarboxylic acid (e-A1) is selected from the group
consisting of terephthalic acid, isophthalic acid, a
naphthalenedicarboxylic acid (NDA), biphenyldicarboxylic acid,
1,5-anthracene dicarboxylic acid, p-terphenylene-4,4''-dicarboxylic
acid, 2,5-pyridine dicarboxylic acid, and mixtures thereof; and/or
the cycloaliphatic dicarboxylic acid (f-A1) is selected from the
group consisting of 1,3-cyclopentanedicarboxylic acid,
1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
2,3-norbornanedicarboxylic acid, 2,6-norbornanedicarboxylic acid,
and mixtures thereof; and/or the lactam and/or the aminocarboxylic
acid (g-A1) are selected from the group consisting of
m-aminobenzoic acid, p-aminobenzoic acid, caprolactam (CL),
.alpha.,.omega.-aminocaproic acid, .alpha.,.omega.-aminoheptanoic
acid, .alpha.,.omega.-aminooctanoic acid,
.alpha.,.omega.-aminononanoic acid, .alpha.,.omega.-aminodecanoic
acid, .alpha.,.omega.-aminoundecanoic acid (AUA), laurolactam (LL),
and .alpha.,.omega.-aminododecanoic acid (ADA).
9. The polyamide molding compound in accordance with claim 1,
wherein the monomers having aromatic structural units for the
transparent polyamides (A1) and (A2) are selected from the group
consisting of terephthalic acid, isophthalic acid,
naphthalenedicarboxylic acid (NDA), biphenyldicarboxylic acid,
4,4'-diphenyl ether dicarboxylic acid,
4,4'-diphenylmethanedicarboxylic acid,
4,4'-diphenylsulfonedicarboxylic acid, 1,5-anthracene dicarboxylic
acid, p-terphenylene-4,4''-dicarboxylic acid,
2,5-pyridinedicarboxylic acid, and xylylenediamine; and the
monomers having aromatic structural units for the transparent
polyamides (A1) and (A2) are selected from the group consisting of
terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic
acid, 2,6-naphthalenedicarboxylic acid, meta-xylylenediamine and
mixtures thereof.
10. The polyamide molding compound in accordance with claim 1,
wherein the polyamide (A1) is selected from the group consisting of
PA MACMI/12, PA MACMT/12, PA MACMI/MACMT/12, PA MACMI/MACMT/MACM12,
PA 6I/6T/MACMI/MACMT, PA 6I/6T/MACMI/MACMT/12, PA 6I/MACMI/, PA
6I/6T/PACMI/PACMT, PA 6I/612MACMI/MACM12, PA
6I/6T/MACMI/MACMT/PACMI/PACMT, PA 6I/6T/MACMI/MACMT/PACMI/PACMT/12,
PA MACMI/MACMT/MACM36, PA MACMI/MACM36, PA MACMT/MACM36, PA
12/PACMI, PA 12/MACMT, PA 6/PACMT, PA 6/PACMI, PA MXDI, PA
MXDI/MXD6, PA MXDI/MXD10, PA MXDI/MXDT, PA MXDI/MACMI, PA
MXDI/MXDT/MACMI/MACMT, PA 6I/6T/BACI/BACT, PA
MACMI/MACMT/BACI/BACT, PA 6I/6T/MACMI/MACMT/BACI/BACT, and mixtures
thereof; and/or the polyamide (A2) is selected from the group
consisting of PA MACM9, PA MACM10, PA MACM11, PA MACM12, PA MACM13,
PA MACM14, PA MACM15, PA MACM16, PA MACM17, PA MACM18, PA MACM36,
PA PACM9, PA PACM10, PA PACM11, PA PACM12, PA PACM13, PA PACM14, PA
PACM15, PA PACM16, PA PACM17, PA PACM18, PA PACM36, PA TMDC9, PA
TMDC10, PA TMDC11, PA TMDC12, PA TMDC13, PA TMDC14, PA TMDC15, PA
TMDC16, PA TMDC17, PA TMDC18, PA TMDC36, PA MACM10/1010, PA
MACM10/PACM10, PA MACM12/1012, PA MACM14/1014, PA PACM10/1010, PA
PACM12/1012, PA PACM14/1014, PA MACM12/PACM12, PA MACM14/PACM14,
MACMI/MACM12, PA MACMT/MACM12, PA MACMI/MACMT/MACM12, PA
MACMI/MACMT/10I/10T/1012, PA 6I/6T/612/MACMI/MACMT/MACM12, PA
6I/6T/612/PACMI/PACMT/PACM12, PA 6I/612/MACMI/MACM12, PA
6T/612/MACMT/MACM12, PA 10T/1012/MACMT/MACM12, PA
10I/1012/MACMI/MACM12, PA
6I/6T/MACMI/MACMT/PACMI/PACMT/MACM12/PACM12, PA
MACMI/PACMI/MACM12/PACM12, PA MACMT/PACMT/MACM12/PACM12, PA
MACMI/PACMT/MACM12/PACM12, PA MACMI/MACM36, PA MACMI/MACMT/MaCM36,
PA 1012/MACMI, PA 1012/MACMT, 1010/MACMI, PA 1010/MACMT, PA
612/MACMT, PA 610/MACMT, PA 612/MACMI, PA 610/MACMI, PA 1012/PACMI,
PA 1012/PACMT, PA 1010/PACMI, PA 1010/PACMT, PA 612/PACMT, PA
612/PACMI, PA 610/PACMT, PA 610/PACMI, and mixtures thereof; and/or
the polyamide mixture (A) comprises or consists of the following
combinations of the polyamides (A1) and (A2): polyamide (A1) PA
MACMI/MACMT/12 and polyamide (A2) PA MACM12; or polyamide (A1) PA
MACMI/MACMT/12 and polyamide (A2) PA MACM10; or polyamide (A1) PA
MACMI/MACMT/12 and polyamide (A2) PA MACM14; or polyamide (A1) PA
MACMI/MACMT/12 and polyamide (A2) PA PACM10; or polyamide (A1) PA
MACMI/MACMT/12 and polyamide (A2) PA PACM14; or polyamide (A1) PA
MACMI/MACMT/12 and polyamide (A2) PA MACM12; or polyamide (A1) PA
MACMI//12 and polyamide (A2) PA MACM12; or polyamide (A1) PA
6I/6T/MACMI/MACMT/MACM12 and polyamide (A2) PA MACM12.
11. The polyamide molding compound in accordance with claim 1,
wherein the polyamide molding compound comprises the following
components: (A) 50 to 95 wt % of a mixture of (A1) 25 to 48%
polyamide PA MACMI/MACMT/12; (A2) 52 to 75% polyamide PA MACM12;
(B) 5 to 50 wt % of at least one glass filler having a refractive
index in the range from 1.510 to 1.539; and (C) 0 to 10 wt % of at
least one additive.
12. The polyamide molding compound in accordance with claim 1,
wherein the at least one glass filler (B) is selected from the
group consisting of glass fibers, ground glass fibers, glass
particles, glass flakes, glass spheres, hollow glass spheres, and
mixtures thereof.
13. The polyamide molding compound in accordance with claim 1,
wherein the glass type of the at least one glass filler (B) is
selected from the group consisting of S-glass, C-glass, and
A-glass.
14. The polyamide molding compound in accordance with claim 1,
wherein the at least one additive (C) is selected from the group
consisting of inorganic and organic stabilizers, monomers,
plasticizers, less than 5 wt % with respect to the total mass of
the polyamide molding compound or to the sum of the components (A)
to (C), semi-crystalline polyamides, impact modifiers, lubricants,
colorants, marking means, photochromic agents, antistatic agents,
demolding means, condensation catalysts, chain regulators,
anti-foaming agents, anti-blocking agents, optical brighteners,
halogen flame retardants, non-halogen flame retardants, natural
sheet silicates, synthetic sheet silicates, nanoscale fillers
having a particle size (d90) of a maximum of 100 nm, and mixtures
thereof.
15. The polyamide molding compound in accordance with claim 1,
wherein component (A1) has a glass transition temperature
determined in accordance with ISO 11357-2 of at least 135.degree.
C.; and/or mixture (A) has a glass transition temperature
determined in accordance with ISO 11357-2 of at least 135.degree.
C.; and/or component (A1) has a glass transition temperature
determined in accordance with ISO 11357-2 of at least 130.degree.
C.; and/or the polyamide molding compound has a glass transition
temperature determined in accordance with ISO 11357-2 of at least
130.degree. C.
16. A molded body comprising a polyamide molding compound in
accordance with claim 1.
17. The molded body in accordance with claim 16, wherein the molded
body is a multilayer molded body.
18. The polyamide molding compound in accordance with claim 5,
wherein the cycloaliphatic diamine (a-A2) is selected from the
group consisting of bis(4-amino-3-methylcyclohexyl)methane,
bis-(4-aminocylcohexyl)methane,
bis-(4-amino-3-ethylcyclohexyl)methane,
bis-(4-amino-3,5,-dimethylcyclohexyl)methane, 2,6-norbornane
diamine or 2,6-bis-(aminomethyl)-norborane, 1,3-diaminocyclohexane,
1,4-diaminocyclohexanediamine, isophorone diamine,
1,3-bis-(aminomethyl)cyclohexane, 1,4-bis-(aminomethyl)cyclohexane,
2,2-(4,4'-diamonodicyclohexyl)propane, and mixtures thereof; and/or
the diamine having aromatic structural unit (b-A2) is a
xylylenediamine; and/or the open-chain aliphatic diamine (c-A2) is
a hexanediamine, and/or the aliphatic dicarboxylic acid (d-A2) is
selected from the group consisting of 1,6-apidic acid,
1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic
acid, 1,12 dedecanedioic acid, 1,13-tridecanedioic acid,
1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid,
1,18-octadecanedioic acid, and mixtures thereof; and/or the
aromatic dicarboxylic acid (e-A2) is selected from the group
consisting of terephthalic acid, isophthalic acid, a
naphthalenedicarboxylic acid (NDA), biphenyldicarboxylic acid,
1,5-anthracene dicarboxylic acid, p-terphenylene-4,4''-dicarboxylic
acid, 2,5-pyridine dicarboxylic acid, and mixtures thereof; and/or
the cycloaliphatic dicarboxylic acid (f-A2) is selected from the
group consisting of 1,3-cyclopentanedicarboxylic acid,
1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
2,3-norbornanedicarboxylic acid, 2,6-norbornanedicarboxylic acid,
and mixtures thereof; and/or the lactam and/or the aminocarboxylic
acid (g-A2) are selected from the group consisting of
m-aminobenzoic acid, p-aminobenzoic acid, caprolactam (CL),
aminocaproic acid, .alpha.,.omega.-aminoheptanoic acid,
.alpha.,.omega.-aminooctanoic acid, .alpha.,.omega.-aminononanoic
acid, .alpha.,.omega.-aminodecanoic acid,
.alpha.,.omega.-aminoundecanoic acid (AUA), laurolactam (LL), and
.alpha.,.omega.-aminododecanoic acid (ADA).
Description
CROSS-REFERENCE TO A RELATED APPLICATION
This patent application claims the benefit of European Patent
Application No. 17 186 918.3, filed on Aug. 18, 2017, the
disclosure of which is incorporated herein by reference in its
entirety for all purposes.
The present invention relates to polyamide molding compounds having
low haze filled with glass, to molded bodies manufactured
therefrom, and to use of same.
Due to their very good optical and mechanical characteristics, the
use of amorphous or microcrystalline polyamide molding compounds is
very widespread for applications in the fields of automotive parts,
electronics, optical components, shields, housings, visible
surfaces, etc.
In order in particular to increase properties such as the
stiffness, strength, deformation reduction, and surface scratch
resistance, fibrous or particulate glass fillers can be admixed to
the molding compounds. As a rule, a deterioration of the optical
properties, in particular of the haze and of the transparency, is
observed in this process.
The approach widespread in the prior art for suppressing a
deterioration of the optical properties is the adaptation of the
refractive index of the glass to that of the polymer. A glass is
proposed for this purpose in EP 2 169 008 A1 whose ranges of
network formers, network modifiers, and intermediate oxides can be
selected as so wide that the refractive index can be set in the
range from 1.510 to 1.540, measured at a wavelength of 589 nm (nD).
The document further describes that the refractive index to be set
for the glass on the addition of the filler to the polymer should
not deviate by more than 0.002 from that of the polymer.
WO 2015/132510 A1 likewise relates to transparent polyamide molding
compounds reinforced with glass fillers. At least one
semi-crystalline polyamide is introduced into the polyamide molding
compound to set the refractive index of the molding compounds
otherwise on the basis of amorphous polyamides. The polyamide
molding compounds in accordance with the claims worked in the
examples have glass transition temperatures of a maximum of
135.degree. C. Higher glass transition temperatures were evidently
not desired since in the discussion of the prior art problems in
the processing of molding compounds, in particular with a material
removal, having glass transition temperatures of >150.degree. C.
formed the subject matter.
The prior art has substantial disadvantages that should be improved
by the present invention. The preparation of a glass having the
accuracy of a refractive index of 0.002 thus requires a substantial
technical effort with respect to a glass composition that is as
exact as possible, with respect to the raw material purity, with
respect to an exact melt homogeneity, and with respect to the
temperature regime to be used in the glass manufacture since these
factors have an influence on the refractive index of the glass.
Such an effort is hardly economically sensible for glasses that
only serve as material for fillers and that should be produced as
inexpensively as possible if a new glass has to be prepared in each
case for a specific polyamide having a specific refractive
index.
Depending on the demands of a given application, there is
frequently the need to vary the components of a polymer matrix to
achieve a specific property profile. As a rule, however, the
refractive index of the polymer thereby changes, whereby a
respective glass adapted thereto would have to be prepared with the
described effort to obtain reinforced molding compounds having good
optical properties.
The present invention pursues the object of providing a polyamide
molding compound on the basis of transparent polyamides reinforced
with glass fillers having a relatively low refractive index, in
particular in the range from 1.510 to 1.539. In this respect, the
polyamide molding compound should have good transparency and a low
haze value with simultaneously good mechanical properties. It was
equally an object of the present invention to provide polyamide
molding compounds having high heat deflection without the
processing properties being degraded.
This object is satisfied by the polyamide molding compounds in
accordance with the invention described herein that comprise or
consist of the following components: (A) 50 to 95 wt % of a mixture
consisting of the polyamides (A1) and (A2), wherein (A1) is at
least one transparent, semi-aromatic polyamide having at least 25
mol % of monomers having aromatic structural units, related to the
total quantity of diamines and dicarboxylic acids in the polyamide
(A1) that is amorphous or microcrystalline; and (A2) is at least
one transparent polyamide having less than 25 mol % of monomers
having aromatic structural units, related to the total quantity of
diamines and dicarboxylic acids in the polyamide (A2) that is
amorphous or microcrystalline; (B) 5 to 50 wt % of at least one
glass filler having a refractive index in the range from 1.510 to
1.539; and (C) 0 to 10 wt % of at least one additive.
The following requirements must be satisfied here: The parts by
weight of the components (A) to (C) add up to 100 wt %. The parts
by weight of the components (A1) and (A2) add up to 100% of
component (A). The content of (A1) in the mixture (A) is >50 wt
%, if the ratio is .DELTA.2/.DELTA.1>1 and the content of (A2)
in the mixture (A) is >50 wt %, if the ratio is
.DELTA.2/.DELTA.1.ltoreq.1 (where .DELTA.1=n(A1)-n(B) and
.DELTA.2=n(B)-n(A2) applies.) The transparent polyamides (A1) and
(A2) have a transparency of at least 90% and a haze of at most 3%.
Mixture (A) has a transparency of at least 88% and a haze of at
most 5%.
Advantageous embodiments of the polyamide molding compound in
accordance with the invention are described herein.
The present invention further relates to molded bodies that
comprise and preferably consist of the polyamide molding compound
in accordance with the invention. These molded bodies are in
particular selected from the group comprising components of
cellular telephones, tablets, housings of electronic devices, trim
parts in vehicles and at home, covers, visible surfaces, backlit
components, shields, containers, vehicle keys, and leisure and
outdoor articles.
Preferred embodiments of these molded bodies are described
herein.
Definitions of Terms
Notation and Abbreviations for Polyamides and their Monomers
In the sense of the present invention, the term "polyamide"
(abbreviation PA) is understood as an umbrella term; it comprises
homopolyamides and copolyamides. The selected notations and
abbreviations for polyamides and their monomers correspond to those
set forth in the ISO standard 16396-1 (2015, (D)). The
abbreviations used there are used as synonyms to the IUPAC names of
the monomers in the following; the following abbreviations for
monomers in particular occur: MACM for
bis(4-amino-3-methylcyclohexyl)methane (also called
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, CAS #6864-37-5);
PACM for bis(4-aminocyclohexyl)methane (also called
4,4'-diaminodicyclohexylmethane, CAS #1761-71-3); TMDC for
bis-(4-amino-3,5-dimethylcyclohexyl)methane (also called
3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane); CAS
#65962-45-0); T for terephthalic acid (CAS #100-21-0); I for
isopththalic acid CAS #121-95-5); BAC for
1,4-bis(aminomethyl)-cyclohexane (CAS #2549-93-1).
Indications of Quantity
The polyamide molding compounds in accordance with the present
invention comprise the components (A) to (C) or preferably
exclusively consist of the components (A) to (C); the requirement
applies here that the components (A) to (C) add up to 100 wt % in
sum. The fixed ranges of the indications of quantity for the
individual components (A) to (C) are to be understood such than an
arbitrary quantity for each of the individual components can be
selected within the specified ranges provided that the strict
provision is satisfied that the sum of all the components (A) to
(C) produces 100 wt %.
Amorphous or Microcrystalline Polyamides
Amorphous or microcrystalline polyamides preferably display a
melting heat of a maximum of 25 J/g, particularly preferably of a
maximum of 22 J/g, very particularly preferably of 0 to 20 J/g at a
heating rate of 20 K/min in dynamic differential scanning
calorimetry (DSC) in accordance with ISO 11357 (2013).
Microcrystalline polyamides also have a melting point in addition
to a glass transition temperature. However, they have a morphology
in which the crystallites have such a small dimension that a plate
manufactured therefrom is still transparent at a thickness of 2 mm,
i.e. its light transmission amounts to at least 90% and its haze to
at most 3%, measured in accordance with ASTM D 1003-13 (2013).
Amorphous polyamides have no melting heat or only very little
melting heat or hardly detectable melting heat in comparison with
the microcrystalline polyamides. The amorphous polyamides
preferably display a melting heat of a maximum of 5 J/g,
particularly preferably of a maximum of 3 J/g, very particularly
preferably of 0 to 1 J/g at a heating rate of 20 K/min in dynamic
differential scanning calorimetry (DSC) in accordance with ISO
11357 (2013).
Amorphous polyamides have no melting point due to their
amorphicity.
In the sense of the present invention, semi-crystalline polyamides
are those polyamides that preferably display a melting heat of more
than 25 J/g, particularly preferably of at most 35 J/g, very
particularly preferably of at least 40 J/g at a heating rate of 20
K/min in dynamic differential scanning calorimetry (DSC) in
accordance with ISO 11357 (2013). A plate manufactured from
semi-crystalline polyamides and having a thickness of 2 mm is not
transparent, i.e. its light transmission is below 90% and/or its
haze is above 3%, measured in each case in accordance with ASTM D
1003-13 (2013).
Transparent Polyamides
In the sense of the present invention a polyamide is transparent
when its light transmission measured according to ASTM D 1003-13
(2013) at plates having a thickness of 2 mm amounts to at least 90%
and when its haze amounts to at most 3%. If transparent polyamides
are spoken of in the following, it is always amorphous or
microcrystalline polyamides that are meant that satisfy the above
definitions with respect to transparency and melting heat.
Haze, Transparency
The haze describes the scattering behavior of a substance; the the
light transmission through the substance. Within the framework of
the present invention, the haze or transparency is understood as
the haze or transparency (total transmission) measured in
accordance with ASTM D1003 on a measuring device Haze Gard Plus of
the company BYK Gardner with CIE light type C at 23.degree. C. at a
molded body manufactured from the polyamide molding compound
(plates of 2 mm thickness with a width and length: 60.times.60
mm).
Refractive Index
The refractive index is abbreviated in the formulas and in the
experimental part by "n". The refractive index is always specified
with respect to the glass filler, in particular glass fibers,
measured at a wavelength of 589 nm. The determination of the
refractive index of glass fillers, in particular of glass fibers,
took place using the Beck's line method and using immersion fluids
with respect to 589 nm based on method B of ISO 489(1999-04). The
refractive index of the polyamides (A1) and (A2) was determined at
plates of a 2 mm thickness (60.times.60.times.2 mm) at a wavelength
of 589 nm and at 23.degree. C. by means of an Abbe refractometer of
Carl Zeiss in accordance with method A of ISO 489 (1999-04).
1-bromonaphthalene was used as the contact fluid.
Component (A)
The polyamide molding compound in accordance with the invention
comprises 50 to 95 wt % of component (A), with respect to the sum
of the components (A) to (C), with it being a mixture consisting of
the polyamides (A1) and (A2). The parts by weight of the components
(A1) and (A2) add up to 100% of component (A). (A1) is here at
least one transparent, semi-aromatic polyamide having at least 25
mol % of monomers having aromatic structural units, related to the
total quantity of diamines and dicarboxylic acids in the polyamide
(A1) and is amorphous or microcrystalline. (A2) is at least one
transparent, semi-aromatic polyamide having less than 25 mol % of
monomers having aromatic structural units, related to the total
quantity of diamines and dicarboxylic acids in the polyamide (A2)
and is amorphous or microcrystalline. The polyamides (A1) and (A2)
are in particular amorphous.
The proportion of the components (A1) in the mixture (A) is greater
than 50 wt % when the following condition is satisfied:
.DELTA.2/.DELTA.1.gtoreq.1 The proportion of the components (A2) in
the mixture (A) is greater than 50 wt % when the following
condition is satisfied: .DELTA.2/.DELTA.1.ltoreq.1 It applies here
that .DELTA.1=n(A1)-n(B) and .DELTA.2=n(B)-n(A2), where n (A1)
stands for the refractive index of the component A1; n (A2) stands
for the refractive index of the component (A2); and n (B) stands
for the refractive index of the glass filler.
The provisions further apply that the transparent polyamides (A1)
and (A2) have a transparency of at least 90% and a haze of at most
3% and that the mixture (A) has a transparency of at least 88% and
a haze of at most 5%.
Preferred embodiments of component (A) will be discussed in the
following.
In accordance with a preferred embodiment of the present invention,
component (A1) or component (A2) is amorphous; particularly
preferably both components are amorphous.
In accordance with a preferred embodiment of the present invention,
the proportion of component (A) in the polyamide molding compound
is in the range from 55 to 90 wt %, particularly preferably 60 to
85 wt %, and in particular preferably 62 to 84.9 wt %, with respect
to the total weight of the polyamide molding compound.
Another preferred embodiment of the present invention provides that
the polyamide mixture (A) consists of 51 to 95 wt %, preferably 55
to 90 wt %, and in particular 60 to 85 wt % polyamide (A1) and of 5
to 49 wt %, particularly preferably 10 to 45 wt %, and in
particular 15 to 40 wt % polyamide (A2) if
.DELTA.2/.DELTA.1>1.
The polymer mixture (A) is preferably composed as follows in
dependence on the ratio .DELTA.2/.DELTA.1 in the range
.DELTA.2/.DELTA.1>1:
TABLE-US-00001 .DELTA.2/.DELTA.1 (A1) [wt %] (A2) [wt %] 1.01 to
1.25 51 to 60 40 to 49 1.26 to 1.69 61 to 71 29 to 39 1.70 to 2.30
72 to 82 18 to 28 2.31 to 20 83 to 95 5 to 17
In accordance with another preferred embodiment of the present
invention, the polyamide mixture (A) consists of 51 to 95 wt %,
preferably 55 to 90 wt %, and in particular 60 to 85 wt % polyamide
(A2) and of 5 to 49 wt %, preferably 10 to 45 wt %, and in
particular 15 to 40 wt % polyamide (A1) if
.DELTA.2/.DELTA.1.ltoreq.1.
The polymer mixture (A) is preferably composed as follows in
dependence on the ratio .DELTA.2/.DELTA.1 in the range
.DELTA.2/.DELTA.1.ltoreq.1:
TABLE-US-00002 .DELTA.2/.DELTA.1 (A1) (A2) 0.71 to 1.00 41 to 49 51
to 59 0.29 to 0.70 24 to 40 60 to 76 0.05 to 0.28 5 to 23 77 to
95
It is further preferred that .DELTA.1 and .DELTA.2 are equal to or
greater than 0.003, are particularly preferably in the range from
0.003 to 0.03, and are in particular in the range from 0.0035 to
0.025.
In accordance with a further preferred embodiment of the present
invention, the transparent polyamides (A1) are made up of the
following monomers: (a-A1) 20 to 100 mol % of cycloaliphatic
diamines, with respect to the total quantity of diamines; (b-A1) 0
to 80 mol % of diamines having aromatic structural units, with
respect to the total quantity of diamines; (c-A1) 0 to 80 mol % of
open-chain cycloaliphatic diamines, with respect to the total
quantity of diamines; (d-A1) 0 to 75 mol % of open-chain aliphatic
dicarboxylic acids, with respect to the total quantity of
dicarboxylic acids; (e-A1) 25 to 100 mol % of aromatic dicarboxylic
acids, with respect to the total quantity of dicarboxylic acids;
(f-A1) 0 to 75 mol % of cycloaliphatic dicarboxylic acids, with
respect to the total quantity of dicarboxylic acids; (g-A1) 0 to 40
wt % of lactams and/or aminocarboxylic acids having 6 to 12 carbon
atoms, with respect to the total quantity of the monomers (a-A1) to
(g-A1), where the sum of the diamines (a-A1), (b-A1), and (c-A1)
produces 100 mol %; where the sum of the dicarboxylic acids (d-A1),
(e-A1), and (f-A1) produces 100 mol %; and where the sum of the
monomers (b-A1) and (e-A1) amounts to at least 25 mol %, with
respect to the sum of the total diamines and of the total
dicarboxylic acids in the polyamide (A1). The content of aromatic
dicarboxylic acids (e-A1) is particularly preferably in the range
from 50 to 100 mol %; the content of open-chain, aliphatic
dicarboxylic acids (d-A1) in the range from 0 to 50 mol %; and the
content of cycloaliphatic dicarboxylic acids (f-A1) in the range
from 0 to 50 mol %, in each case with respect to the total quantity
of dicarboxylic acids. Further preferably, the content of
cycloaliphatic diamines (a-A1) is in the range from 50 to 100 mol
%; the content of open-chain, aliphatic diamines (c-A1) in the
range from 0 to 50 mol %; and the content of cycloaliphatic
diamines (b-A1) in the range from 0 to 50 mol %, in each case with
respect to the total quantity of diamines. Very particularly
preferably, (A1) is free of diamines (b-A1).
In accordance with another preferred embodiment of the present
invention, the transparent polyamide (A1) comprises at least 27 mol
%, preferably at least 30 mol %, particularly preferably in the
range from 25 to 100 mol %, 27 to 80 mol %, or 30 to 60 mol % of
monomers having aromatic structural units, with respect to the
total quantity of diamines and dicarboxylic acids in the polyamide
(A1).
Another preferred embodiment of the present invention provides that
the transparent polyamides (A2) are made up of the following
monomers: (a-A2) 20 to 100 mol % of cycloaliphatic diamines, with
respect to the total quantity of diamines; (b-A2) 0 to less than 50
mol % of diamines having aromatic structural units, with respect to
the tot-AI quantity of diamines; (c-A2) 0 to 80 mol % of open-chain
aliphatic diamines, with respect to the total quantity of diamines;
(d-A2) 20 to 100 mol % of open-chain aliphatic dicarboxylic acids,
with respect to the total quantity of dicarboxylic acids; (e-A2) 0
to less than 50 mol % of aromatic dicarboxylic acids, with respect
to the total quantity of dicarboxylic acids; (f-A2) 0 to 80 mol %
of cycloaliphatic dicarboxylic acids, with respect to the total
quantity of dicarboxylic acids; (g-A2) 0 to 40 wt % of lactams
and/or aminocarboxylic acids having 6 to 12 carbon atoms, with
respect to the total quantity of the monomers (a-A2) to (g-A2),
where the sum of the diamines (a-A2), (b-A2), and (c-A2) produces
100 mol %; where the sum of the dicarboxylic acids (d-A2), (e-A2),
and (f-A2) produces 100 mol %; and where the sum of the monomers
(b-A2) and (e-A2) amounts to less than 25 mol %, with respect to
the sum of the total diamines and of the total dicarboxylic acids
in the polyamide (A2). The content of open-chain aliphatic
dicarboxylic acids (d-A2) is particularly preferably in the range
from 60 to 100 mol % and the content of aromatic dicarboxylic acids
(e-A2) in the range from 0 to 40 mol %, in each case with respect
to the total quantity of dicarboxylic acids, with (A2) being free
of dicarboxylic acids (f-A2). It is further particularly preferred
for the content of cycloaliphatic diamines (a-A2) to be in the
range from 60 to 100 mol % and for the content of open-chain,
aliphatic diamines (c-A2) to be in the range from 0 to 40 mol %,
respectively with respect to the total quantity of diamines, with
(A2) being free of diamines (b-A2) and preferably being free of
lactams and/or aminocarboxylic acids (g-A2).
In accordance with a further preferred embodiment of the present
invention, the transparent polyamide (A2) comprises at most 23 mol
%, preferably at most 20 mol %, particularly preferably in the
range from 0 to 23 mol %, 0 to 20 mol %, or 0 to 15 mol % of
monomers having aromatic structural units, with respect to the
total quantity of diamines and dicarboxylic acids in the polyamide
(A2). (A2) is very particularly preferably free of diamines (b-A2)
and free of dicarboxylic acids (e-A2).
In accordance with another preferred embodiment of the present
invention, the monomers having aromatic structural units for the
transparent polyamides (A1) and (A2) are selected from the group
comprising terephthalic acid, isophthalic acid,
naphthalenedicarboxylic acid (NDA), in particular
1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic
acid, biphenyldicarboxylic acids, in particular
biphenyl-2,2'-dicarboxylic acid (diphenic acid),
4,4'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid,
4,4'-diphenyl ether dicarboxylic acid,
4,4'-diphenylmethanedicarboxylic acid, and
4,4-diphenylsulfonedicarboxylic acid, 1,5-anthracene dicarboxylic
acid, p-terphenylene-4,4''-dicarboxylic acid, and 2,5-pyridine
dicarboxylic acid, xylylenediamine, in particular
meta-xylylenediamine, and para-xylylenediamine, and mixtures
thereof.
A further preferred embodiment of the present invention provides
that the monomers having aromatic structures for the transparent
polyamides (A1) and (A2) are selected solely from the group
comprising terephthalic acid, isophthalic acid,
1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
and meta-xylylenediamine, and mixtures thereof.
Another preferred embodiment of the invention provides that the
polyamide molding compound comprises exactly one polyamide (A1). In
accordance with a further preferred embodiment of the present
invention, the polyamide molding compound comprises exactly one
polyamide (A2). It is particularly preferred that the polyamide
molding compound comprises exactly one polyamide (A1) and exactly
one polyamide (A2).
Another preferred embodiment of the present invention provides that
the cycloaliphatic diamine (a-A1) and/or (a-A2) is/are selected
from the group comprising bis(4-amino-3-methylcyclohexyl)methane
(MACM), bis-(4-aminocyclohexyl)methane (PACM),
bis-(4-amino-3-ethylcyclohexyl)methane,
bis-(4-amino-3,5-dimethylcyclohexyl)methane, 2,6-norbornane diamine
(2,6-bis-(aminomethyl)norbornane), 1,3-diaminecyclohexane,
1,4-diaminocyclohexanediamine, isophorone diamine,
1,3-bis-(aminomethyl)cyclohexane, 1,4-bis-(aminomethyl)cyclohexane,
2,2-(4,4'-diaminodicyclohexyl)propane, and mixtures thereof. The
cycloaliphatic diamines (a-A1) and/or (a-A2) are particularly
preferably selected from the group comprising
bis(4-amino-3-methylcyclohexyl)methane (MACM) and
bis-(4-aminocyclohexyl)methane (PACM), and mixtures thereof.
In accordance with another preferred embodiment of the present
invention, the aromatic diamine (b-A1) and/or (b-A2) is/are
selected from the group comprising xylylenediamine, in particular
meta-xylylenediamine, and para-xylylenediamine, and mixtures
thereof. The diamines having aromatic structural units (b-A1)
and/or (b-A2) are particularly preferably selected from
meta-xylylenediamine.
In accordance with another preferred embodiment, the diamine (c-A1)
and/or (c-A2) is selected from the group comprising
1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine,
hexanediamine, in particular 1,6-hexanediamine,
2,2,4-trimethyl-1,6-hexamethylenediamine,
2,4,4-trimethyl-1,6-hexamethylenediamine, nonanediamine, in
particular 1,9-nonanediamine, 2-methyl-1,8-octanediamine,
1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine,
1,13-tridecanediamine, 1,14-tetradecanediamine,
1,18-octadecanediamine, and mixtures thereof. The open-chain,
aliphatic diamines (c-A1) and/or (c-A2) are particularly preferably
selected from the group comprising diamines having 6 to 10 carbon
atoms, in particular 1,6-hexanediamine, 1,9-nonanediamine,
1,10-decanediamine, and mixtures thereof.
A further preferred embodiment of the present invention provides
that the aliphatic dicarboxylic acid (d-A1) and/or (d-A2) is
selected from the group comprising 1,6-apidic acid, 1,9-nonanedioic
acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12
dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic
acid, 1,16-hexadecanedioic acid, 1,18-octadecanedioic acid, and
mixtures thereof. The open-chain, aliphatic dicarboxylic acids
(d-A1) and/or (d-A2) are particularly preferably selected from the
group comprising dicarboxylic acids having 6 to 12 carbon atoms, in
particular 1,6-hexanedioic acid, 1,10-decanedioic acid,
1,12-dodecanedioic acid, and mixture thereof.
In accordance with a further preferred embodiment of the present
invention, the aromatic dicarboxylic acid (e-A1) and/or (e-A2) are
selected from the group comprising terephthalic acid, isophthalic
acid, naphthalenedicarboxylic acid (NDA), in particular
1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic
acid, biphenyldicarboxylic acid, in particular
biphenyl-2,2'-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid,
3,3'-diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic
acid, 4,4'-diphenylmethanedicarboxylic acid, and
4,4'-diphenylsulfonedicarboxylic acid, 1,5-anthracene dicarboxylic
acid, p-terphenylene-4,4'-dicarboxylic acid, and 2,5-pyridine
dicarboxylic acid, and mixtures thereof. The aromatic dicarboxylic
acids (e-A1) and/or (e-A2) are particularly preferably selected
from the group comprising terephthalic acid, isophthalic acid, and
mixtures thereof.
A further preferred embodiment of the present invention provides
that the cycloaliphatic dicarboxylic acid (f-A1) and/or (f-A2)
is/are selected from the group comprising
1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic
acid, 1,4-cyclohexanedicarboxylic acid, 2,3-norbornanedicarboxylic
acid, 2,6-norbornanedicarboxylic acid, and mixtures thereof. The
cycloaliphatic dicarboxylic acids (f-A1) and/or (f-A2) are
particularly preferably selected from the group comprising
1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic
acid, and mixtures thereof.
In accordance with a further preferred embodiment of the present
invention, the lactam and/or the .alpha.,.omega.-aminocarboxylic
acids (g-A1) and/or (g-A2) is/are selected from the group
comprising m-aminobenzoic acid, p-aminobenzoic acid, caprolactam
(CL), .alpha.,.omega.-aminocaproic acid,
.alpha.,.omega.-aminoheptanoic acid, .alpha.,.omega.-aminooctanoic
acid, .alpha.,.omega.-aminononanoic acid,
.alpha.,.omega.-aminodecanoic acid, .alpha.,.omega.-aminoundecanoic
acid (AUA), laurolactam (LL), and .alpha.,.omega.-aminododecanoic
acid (ADA); caprolactam, .alpha.,.omega.-aminocaproic acid,
laurolactam, .alpha.,.omega.-aminoundecanoic acid, and
.alpha.,.omega.-aminododecanoic acid, and mixtures thereof are
particularly preferred. The lactams and/or aminocarboxylic acids
(g-A1) and/or (g-A2) are preferably selected from the group
comprising caprolactam, aminocaproic acid, aminoundecanoic acid,
laurolactam, and aminododecanoic acid, and mixtures thereof.
A further preferred embodiment of the present invention provides
that the cycloaliphatic diamine (a-A1) and/or (a-A2) is selected
from the group comprising bis(4-amino-3-methylcyclohexyl)methane,
bis-(4-aminocyclohexyl)methane,
bis-(4-amino-3-ethylcyclohexyl)methane,
bis-(4-amino-3,5,-dimethylcyclohexyl)methane, 2,6-norbornane
diamine, 1,3-diaminecyclohexane, 1,4-diaminocyclohexanediamine,
isophorone diamine, 1,3-bis-(aminomethyl)cyclohexane,
1,4-bis-(aminomethyl)cyclohexane,
2,2-(4,4'-diaminodicyclohexyl)propane, and mixtures thereof and the
aromatic diamine (b-A1) and/or (b-A2) is/are selected from the
group comprising xylylenediamine, in particular
meta-xylylenediamine and para-xylylenediamine, and mixtures
thereof, and the diamine (c-A1) and/or (c-A2) is/are selected from
the group comprising hexanediamine, in particular
1,6-hexanediamine, nonanediamine, in particular 1,9-nonanediamine,
1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine,
1,13-tridecanediamine, 1,14-tetradecanediamine,
1,18-octadecanediamine, and mixtures thereof, and the aliphatic
dicarboxylic acid (d-A1) and/or (d-A2) is selected from the group
comprising 1,6-hexanedioic acid, 19,-nonanedioic acid,
1,10-decanedioic acid, 1,11-undecanedioic aic, 1,12-dodecanedioic
acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid,
1,16-hexadecanedioic acid, 1-18, octadecanedioic acid, and mixtures
thereof, and the aromatic dicarboxylic acid (e-A1) and/or (e-A2)
is/are selected from the group comprising terephthalic acid,
isopththalic acid, naphthalenedicarboxylic acid (NDA), in
particular 1,5-naphthalenedicarboxylic acid and
2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acids, in
particular biphenyl-2,2'-dicarboxylic acid,
4,4'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid,
4,4'-diphenyl ether dicarboxylic acid,
4,4'-diphenylmethanedicarboxylic acid, and
4,4'-diphenylsulfonedicarboxylic acid, 1,5-anthracenedicarboxylic
acid, p-terephenylene-4,4''-dicarboxylic acid, and
2,5-pyridinedicarboxylic acid, and mixtures thereof, and the
cycloaliphatic dicarboxylic acid (f-A1) and/or (f-A2) is/are
selected from the group comprising 1,3-cyclohexanedicarboxylic
acid, 1,4-cyclohexanedicarboxylic acid, and mixtures thereof, and
the lactam and/or the .alpha.,.omega.-aminocarboxylic acids (g-A1)
and/or (g-A2) is/are selected from the group comprising
m-aminobenzoic acid, p-aminobenzoic acid, caprolactam (CL),
.alpha.,.omega.-aminocaproic acid, .alpha.,.omega.-aminoheptanoic
acid, .alpha.,.omega.-aminooctanoic acid,
.alpha.,.omega.-aminononanoic acid, .alpha.,.omega.-aminodecanoic
acid, .alpha.,.omega.-aminoundecanoic acid (AUA), laurolactam (LL),
and .alpha.,.omega.-aminododecanoic acid (ADA); caprolactam,
.alpha.,.omega.-aminocaproic acid, laurolactam,
.alpha.,.omega.-aminoundecanoic acid, and
.alpha.,.omega.-aminododecanoic acid, and mixtures thereof are
particularly preferred.
The cycloaliphatic diamines (a-A1) are particularly preferably
selected from the group comprising
bis-4(-amino-3-methylcyclohexyl)methane (MACM) and
bis(4-aminocyclohexyl)methane (PACM) and mixtures thereof and the
diamines having aromatic structural units (b-A1) are selected from
the group comprising meta-xylylenediamine and para-xylylenediamine
and mixtures thereof, and the open-chain, aliphatic diamines (c-A1)
are selected from the group comprising diamines having 6 to 10
carbon atoms, in particular 1,6-hexanediamine, 1,9-nonanediamine,
1,10-decandediamine, and mixtures thereof, and the open-chain
aliphatic dicarboxylic acids (d-A1) are selected from the group
comprising dicarboxylic acids having 6 to 12 carbon atoms, in
particular 1,6-hexanedioic acid, 1,10-decanedioic acid,
1,12-dodecanedioic acid, and mixtures thereof, and the aromatic
dicarboxylic acids (e-A1) are selected from the group comprising
terephthalic acid, isophthalic acid, and mixtures thereof, and the
cycloaliphatic dicarboxylic acids (f-A1) are selected from the
group comprising 1,3-cyclohexanedicarboxylic acid and
1,4-cyclohexanedicarboxylic acid, and mixtures thereof, and the
lactams and/or aminocarboxylic acids (g-A1) are selected from the
group comprising caprolactam, aminocaproic acid, aminoundecanoic
acid, laurolactam, and aminododecanoic acid, and mixtures
thereof.
The cycloaliphatic diamines (a-A2) are further particularly
preferably selected from the group comprising
bis-4(-amino-3-methylcyclohexyl)methane (MACM) and
bis(4-aminocyclohexyl)methane (PACM) and mixtures thereof and the
diamines having aromatic structural units (b-A2) are selected from
the group comprising meta-xylylenediamine and para-xylylenediamine
and mixtures thereof, and the open-chain, aliphatic diamines (c-A2)
are selected from the group comprising diamines having 6 to 10
carbon atoms, in particular 1,6-hexanediamine, 1,9-nonanediamine,
1,10-decandediamine, and mixtures thereof, and the open-chain
aliphatic dicarboxylic acids (d-A2) are selected from the group
comprising dicarboxylic acids having 6 to 12 carbon atoms, in
particular hexanedioic acid, 1,10-decanedioic acid,
1,12-dodecanedioic acid, and mixtures thereof, and the aromatic
dicarboxylic acids (e-A2) are selected from the group comprising
terephthalic acid, isophthalic acid, and mixtures thereof, and the
cycloaliphatic dicarboxylic acids (f-A2) are selected from the
group comprising 1,3-cyclohexanedicarboxylic acid and
1,4-cyclohexanedicarboxylic acid, and mixtures thereof, and the
lactams and/or aminocarboxylic acids (g-A2) are selected from the
group comprising caprolactam, aminocaproic acid, aminoundecanoic
acid, laurolactam, and aminododecanoic acid, and mixtures
thereof.
In accordance with a further preferred embodiment of the present
invention, the polyamide (A1) is selected from the group comprising
PA MACMI/12, PA MACMI/1012, PA MACMT/12, PA MACMI/MACMT/12, PA
MACMI/MACMT, PA MACMI/MACMT/MACM12, PA 6I/6T/MACMI/MACMT, PA
6I/6T/MACMI/MACMT/12, PA 6I/MACMI, PA 6I/6T/PACMI/PACMT, PA
6I/612/MACMI/MACM12, PA 6T/612/MACMT/MACM12, PA
6I/6T/612/MACMI/MACMT/MACM12, PA 6I/6T/MACMI/MACMT/PACMI/PACMT, PA
6I/6T/MACMI/MACMT/PACM I/PACMT/12, PA MACMI/MACMT/MACM36, PA
MACMI/MACM36, PA MACMT/MACM36, PA 12/PACMI, PA 12/MACMT, PA
6/PACMT, PA 6/PACMI, PA MXDI, PA MXDI/MXD6, PA MXDI/MXD10, PA
MXDI/MXDT, PA MXDI/MACMI, PA MXDI/MXDT/MACMI/MACMT, PA
6I/6T/BACI/BACT, PA MACMI/MACMT/BACI/BACT, PA
6I/6T/MACMI/MACMT/BACI/BACT and mixtures thereof, wherein these
polyamides comprise at least 25 mol % of monomers having aromatic
structural units, with respect to the total quantity of diamines
and dicarboxylic acids.
Another preferred embodiment of the present invention provides that
the polyamide (A2) is selected from the group PA MACM9, PA MACM10,
PA MACM11, PA MACM12, PA MACM13, PA MACM14, PA MACM15, PA MACM16,
PA MACM17, PA MACM18, PA MACM36, PA PACM9, PA PACM10, PA PACM11, PA
PACM12, PA PACM13, PA PACM14, PA PACM15, PA PACM16, PA PACM17, PA
PACM18, PA PACM36, PA TMDC9, PA TMDC10, PA TMDC11, PA TMDC12, PA
TMDC13, PA TMDC14, PA TMDC15, PA TMDC16, PA TMDC17, PA TMDC18, PA
TMDC36 or copolyamides such as PA MACM10/1010, PA MACM10/PACM10, PA
MACM12/1012, PA MACM14/1014, PA PACM10/1010, PA PACM12/1012, PA
PACM14/1014, PA MACM12/PACM12, PA MACM14/PACM14, PA MACMI/MACM12,
PA MACMT/MACM12, PA MACMI/MACMT/MACM12, PA MACMI/MACMT/10/10T/1012,
PA 6I/6T/612/MACMI/MACMT/MACM12, PA 6I/6T/612/PACMI/PACMT/PACM12,
PA 6I/612/MACMI/MACM12, PA 6T/612/MACMT/MACM12, PA
10T/1012/MACMT/MACM12, PA 10I/1012/MACMI/MACM12, PA
6I/6T/MACMI/MACMT/PACMI/PACMT/MACM12/PACM12, PA
MACMI/PACMI/MACM12/PACM12, PA MACMT/PACMT/MACM12/PACM12, PA
MACMI/PACMT/MACM12/PACM12, PA MACMI/MACM36, PA MACMI/MACMT/MaCM36,
PA 1012/MACMI, PA 1012/MACMT, 1010/MACMI, PA 1010/MACMT, PA
612/MACMT, PA 610/MACMT, PA 612/MACMI, PA 610/MACMI, PA 1012/PACMI,
PA 1012/PACMT, PA 1010/PACMI, PA 1010/PACMT, PA 612/PACMT, PA
612/PACMI, PA 610/PACMT, PA 610/PACMI and mixtures thereof, wherein
these polyamides comprise less than 25 mol % of monomers having
aromatic structural units, with respect to the total quantity of
diamines and dicarboxylic acids.
The polyamide mixture (A) particularly preferably comprises or
consists of the following combinations of the polyamides (A1) and
(A2): polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA MACM12
or polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA MACM10 or
polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA MACM14 or
polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA PACM10 or
polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA PACM14 or
polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA MACM12 or
polyamide (A1) PA MACMI/12 and polyamide (A2) PA MACM12 or
polyamide A1 PA 6I/6T/MACMI/MACMT/MACM12 and polyamide (A2) PA
MACM12.
In accordance with a further preferred embodiment of the present
invention, component (A1) has a glass transition temperature
determined in accordance with ISO 11357-2 of at least 135.degree.
C., preferably at least 140.degree. C., particularly preferably
145.degree. C., and in particular preferably 150.degree. C.
Another preferred embodiment of the present invention provides that
component (A2) has a glass transition temperature determined in
accordance with ISO 11357-2 of at least 135.degree. C., preferably
at least 140.degree. C., particularly preferably 145.degree. C.,
and in particular preferably 150.degree. C.
In accordance with a further preferred embodiment of the present
invention, the mixture (A) has a glass transition temperature
determined in accordance with ISO 11357-2 of at least 130.degree.
C., preferably at least 135.degree. C., particularly preferably
140.degree. C., and in particular preferably 145.degree. C.
A further preferred embodiment of the present invention provides
that the component (A1) has a glass transition temperature
determined in accordance with ISO 11357-2 of at least 135.degree.
C., preferably at least 140.degree. C., particularly preferably
145.degree. C., and in particular preferably 150.degree. C. and the
component (A2) has a glass transition temperature determined in
accordance with ISO 11357-2 of at least 135.degree. C., preferably
at least 140.degree. C., particularly preferably 145.degree. C.,
and in particular preferably 150.degree. C. and the mixture (A) has
a glass transition temperature determined in accordance with ISO
11357-2 of at least 130.degree. C., preferably at least 135.degree.
C., particularly preferably 140.degree. C., and in particular
preferably 145.degree. C.
In accordance with a further preferred embodiment of the present
invention, the polyamide molding compound has a glass transition
temperature determined in accordance with ISO 11357-2 of at least
130.degree. C., preferably at least 135.degree. C., particularly
preferably 140.degree. C., and in particular preferably 145.degree.
C.
In accordance with another preferred embodiment of the present
invention, the polyamides (A1) and/or (A2) comprise at most 30 wt
%, particularly preferably at most 20 wt % of lactams and
aminocarboxylic acids; they are in particular free of lactams and
aminocarboxylic acids, in particular free of aminoundecanoic
acid.
In accordance with another preferred embodiment of the present
invention, the at least one polyamide (A2) is free of monomers
having aromatic structural units and/or free of lactams and
aminocarboxylic acids, in particular free of aminoundecanoic
acid.
The components (A1) and (A2) preferably have a relative viscosity,
measured in accordance with ISO 307 (2007) in a solution of 0.5 g
polymer in 100 ml m-cresol at 20.degree. C., in the range from 1.35
to 2.40, particularly preferably from 1.40 to 1.90, and very
particular preferably from 1.42 to 1.80.
Component (B)
The molding compound in accordance with the invention comprises as
a component (B) at least one glass filler.
The glass filler (B) is preferably included in the polyamide
molding compound at 10 to 40 wt %, particularly preferably at 15 to
35 wt % and very particularly preferably at 15 to 30 wt %, with
these indications of quantity relating to the polyamide molding
compound resulting at 100 wt % from the components (A), (B), and
(C).
The glass filler is preferably selected from the group comprising
glass fibers, ground glass fibers, glass particles, glass flakes,
glass spheres, hollow glass spheres, or comprising combinations of
the aforesaid. Combinations of fillers are preferably only used
when the refractive indices do not differ between the filler
categories.
If glass spheres or glass particles are selected as the glass
filler (B), their mean diameter amounts to 0.3 to 100 .mu.m,
preferably 0.7 to 30 .mu.m, particularly preferably 1 to 10
.mu.m.
The at least one glass filler (B) preferably has a refractive
index, measured at a wavelength of 589 nm, of 1.511 to 1.538,
preferably of 1.513 to 1.535, and in particular of 1.515 to
1.530.
A preferred embodiment of the present invention provides that the
glass type of the at least one glass filler (B) is selected from
the group comprising S-glass, A-glass and C-glass, in particular
S-glass, and mixtures of glass having substantially the same
refractive index. The term "substantially the same refractive
index" is understood in that the difference in the refractive index
of the glass species forming the mixture is .ltoreq.0.01,
preferably .ltoreq.0.005.
A preferred embodiment provides that the glass filler (component
(B)) has the following composition: 61 to 75 wt %, in particular 62
to 72 wt %, silica, 0 to 25 wt %, in particular 20 to 25 wt %,
alumina, 5 to 15 wt %, in particular 6 to 12 wt %, calcium oxide
and/or magnesium oxide, 0 to 6 wt % boron oxide, and 0 to 20 wt %
further components such as metal oxides of sodium, potassium,
lithium, titanium, zinc, zirconium, iron. It is in particular
preferred if the glass filler is free of calcium oxide and if the
magnesium oxide content is in the range from 8 to 11 wt %.
Preferred glass fillers in accordance with the present invention
are glass fibers.
In accordance with another preferred embodiment, component (B)
comprises A-glass fibers and particularly preferably consists
thereof. A-glass fibers comprise 63 to 72% silica, 6 to 10% calcium
oxide, 14 to 16% sodium oxide and potassium oxide, 0 to 6% alumina,
0 to 6% boron oxide, and 0 to 4% magnesium oxide. Further
components such as fluorine, titanium oxide and iron oxide can be
present in quantities of 0 to 2 wt %.
Another preferred embodiment provides that component (B) comprises
and particularly preferably consists of C-glass fibers. C-glass
fibers comprise 64 to 68% silica, 11 to 15% calcium oxide, 7 to 10%
sodium oxide and potassium oxide, 3 to 5% alumina, 4 to 6% boron
oxide, and 2 to 4% magnesium oxide. Further components such as
barium oxide and iron oxide can be present in quantities of 0 to 2
wt %.
Component (B) is a high strength glass fiber or so-called S-glass
fiber in accordance with a preferred embodiment. This is preferably
based on the ternary system silica-alumina-magnesium oxide or on
the quaternary system silica-alumina-magnesium oxide-calcium oxide,
with a composition of 58 to 70 wt % silica (SiO.sub.2), 15 to 30 wt
% alumina (Al.sub.2O.sub.3), 5 to 15 wt % magnesium oxide (MgO), 0
to 10 wt % calcium oxide (CaO), and 0 to 2 wt % further oxides such
as zirconia (ZrO.sub.2), boron oxide (B.sub.2O.sub.3), titanium
dioxide (TiO.sub.2), iron oxide (Fe.sub.2O.sub.3), sodium oxide,
potassium oxide, or lithium oxide (Li.sub.2O) being preferred.
In accordance with a further preferred embodiment, the high
strength glass fiber has a composition of 60 to 67 wt % silica
(SiO.sub.2), 20 to 28 wt % alumina (Al.sub.2O.sub.3), 7 to 12 wt %
magnesium oxide (MgO), 0 to 9 wt % calcium oxide (CaO), and 0 to
1.5 wt % further oxides such as zirconia (ZrO.sub.2), boron oxide
(B.sub.2O.sub.3), titanium dioxide (TiO.sub.2), iron oxide
(Fe.sub.2O.sub.3), sodium oxide, potassium oxide, or lithium oxide
(Li.sub.2O).
It is in particular preferred if the high strength glass fiber has
the following composition: 62 to 66 wt % silica (SiO.sub.2), 22 to
27 wt % alumina (Al.sub.2O.sub.3), 8 to 12 wt % magnesium oxide
(MgO), 0 to 5 wt % calcium oxide (CaO), 0 to 1 wt % further oxides
such as zirconia (ZrO.sub.2), boron oxide (B.sub.2O.sub.3),
titanium dioxide (TiO.sub.2), iron oxide (Fe.sub.2O.sub.3), sodium
oxide, potassium oxide, or lithium oxide (Li.sub.2O).
The high strength glass fibers (S-glass fibers) preferably have a
tensile strength of at least 3700 MPa, preferably of at least 3800
or 4000 MPa and/or an elongation at break of at least 4.8%,
preferably of at least 4.9 or 5.0% and/or a modulus of elasticity
of more than 75 GPa, preferably of more than 78 or 80 GPa, with
these three glass properties being determined at single fibers
(pristine single filaments) having a diameter of 10 .mu.m and a
length of 12.7 mm at a temperature of 23.degree. C. and at a
relative humidity of 50%.
Specific examples for these high strength glass fibers are S-glass
fibers of Owens Corning having 995 black wash, T-glass fibers of
Nittobo, HiPertex of 3B, HS4 glass fibers of Sinoma Jinhing
Fiberglass, R-glass fibers of Vetrotex, and S-1 and S-2 glass
fibers of AGY.
The above-named glass fibers can be present in the form of short
fibers, preferably in the form of cut glass product having a length
in the range from 0.2 to 20 mm, or in the form of rovings. The
glass fibers furthermore preferably have a circular or non-circular
cross-sectional area.
Glass fibers having a circular cross-section, that is, round glass
fibers, typically have a diameter in the range from 5 to 20 .mu.m,
preferably in the range from 6 to 17 .mu.m, and particularly
preferably in the range from 6 to 13 .mu.m. They are preferably
used as short glass fibers (cut glass product having a length of
0.2 to 20 mm, preferably 2 to 12 mm).
With flat glass fibers, that is, glass fibers having a non-circular
cross-sectional area, they are preferably used with a dimensional
ratio of the main cross-sectional axis to the secondary
cross-sectional axis perpendicular thereto of more than 2,
preferably of 2 to 8, in particular of 2.5 to 5.0. These so-called
flat glass fibers have an oval cross-sectional area, an elliptical
cross-sectional area, an elliptical cross-sectional surface
provided with constriction(s) (so-called "cocoon" fibers),
polygonal, rectangular or almost rectangular cross-sectional
surface.
A further characterizing feature of the flat glass fibers used is
that the length of the main cross-sectional axis preferably lies in
the range from 6 to 40 .mu.m, in particular in the range from 15 to
30 .mu.m, and the length of the secondary cross-sectional axis lies
in the range from 3 to 20 .mu.m, in particular in the range from 4
to 10 .mu.m. The flat glass fibers here have a packing density that
is as high as possible, i.e. the cross-sectional area of the glass
fibers fills an imaginary rectangle surrounding the glass fiber
cross-section as exactly as possible at at least 70%, preferably at
least 80%, and in particularly preferably at at least 85%.
The glass fibers are preferably provided with a black wash that is
suitable for the respective thermoplastic, in particular for
polyamide, for example comprising a bonding agent on the basis of
an aminosilane compound or an epoxysilane compound.
The glass fibers used as a roving in accordance with a further
preferred embodiment have a diameter of 8 to 20 .mu.m, preferably
of 12 to 18 .mu.m, with the cross-section of the glass fibers being
able to be round, oval, elliptical, elliptically provided with
constriction(s), polygonal, rectangular, or almost rectangular.
Component (C)
The polyamide molding compound in accordance with the invention
furthermore comprises from 0 to 10 wt % of the component (C), with
respect to the sum of the components (A) to (C).
In accordance with a preferred embodiment of the present invention,
the proportion of component (C) in the polyamide molding compound
is in the range from 0 to 7 wt %, particularly preferably 0 to 5 wt
%, and particularly preferably 0.1 to 3.0 wt %, in each case with
respect to the sum of the components (A) to (C).
A further preferred embodiment provides that the at least one
additive (C) is selected from the group comprising inorganic and
organic stabilizers, in particular antioxidants, antiozonants, heat
stabilizers, light protection means, UV stabilizers, UV absorbers,
or UV blockers, monomers, in particular lactams, plasticizers, up
to less than 5 wt % with respect to the total mass of the polyamide
molding compound of semi-crystalline polyamides, in particular
polyamide PA 12, impact modifiers, lubricants, colorants, marking
means, photochromic agents, demolding means, condensation
catalysts, chain regulators, in particular monofunctional
carboxylic acids or amines, anti-foaming agents, anti-blocking
agents, optical brighteners, non-halogen flame retardants, natural
sheet silicates, synthetic sheet silicates, nanoscale fillers
having a particle size of a maximum of 100 nm, and mixtures
thereof.
The use of additives to component (C) must in particular be given
special attention with respect to the obtaining of transparency.
Only those additives may preferably be introduced into the molding
compound that have no negative effects or only small negative
effects on the transmission and on the haze of the molding
compound. The molding compound in accordance with the invention
here preferably only comprises the following components (C)
selected from the group comprising inorganic and organic
stabilizers, in particular antioxidants, antiozonants, heat
stabilizers, light protection means, UV stabilizers, UV absorbers
or UV blockers, monomers, lubricants, colorants, marking means,
demolding means, condensation catalysts, chain regulators, in
particular monofunctional carboxylic acids or amines, anti-foaming
agents, anti-blocking agents, optical brighteners, in a quantity of
0.1 to 3.0 wt %, with respect to the sum of components (A) to
(C).
Polyamide Molding Compound
A preferred embodiment of the present invention provides that the
proportion of component (A) in the polyamide molding compound is in
the range from 55 to 90 wt %, preferably 60 to 85 wt %, and
particularly preferably 62 to 84.9 wt %, with respect to the sum of
the components (A) to (C), and the proportion of component (B) in
the polyamide molding compound is in the range from 10 to 40 wt %,
preferably 15 to 35 wt %, and particularly preferably 15 to 30 wt
%, with respect to the sum of the components (A) to (C), and the
proportion of component (C) in the molding compound is in the range
from 0 to 7 wt %, preferably 0 to 5 wt %, and particularly
preferably 0.1 to 3.0 wt %, with respect to the sum of the
components (A) to (C).
Another preferred embodiment of the present invention further
provides that the polyamide molding compound does not have any
other components than the components (A) to (C).
In accordance with another preferred embodiment of the present
invention, the transparency measured in accordance with ASTM D1003
at a molded body (plate with the dimension 60.times.60.times.2 mm)
produced from the polyamide molding compound amounts to at least
80%, preferably at least 85%, and particularly preferably at least
88%.
In accordance with another preferred embodiment of the present
invention, the transparency measured in accordance with ASTM D
10003 at a molded body (plate with a dimension 60.times.60.times.2
mm) containing 20 wt % glass filler B, preferably in the form of
glass fibers, in particular in the form of S-glass fibers, amounts
to at least 80%, preferably at least 85%, and particularly
preferably at least 88%.
A further preferred embodiment provides that the haze measured in
accordance with ASTM D1003 at a molded body (plate with the
dimension 60.times.60.times.2 mm) produced from the polyamide
molding compound amounts to a maximum of 40%, preferably a maximum
of 35%, particularly preferably to a maximum of 25% and very
particularly preferably a maximum of 20%.
Another preferred embodiment provides that the haze measured in
accordance with ASTM D 10003 at a molded body made from polyamide
molding compound (plate with a dimension 60.times.60.times.2 mm)
containing 20 wt % glass filler (B), preferably in the form of
glass fibers, in particular in the form of S-glass fibers, amounts
to a maximum of 30%, preferably a maximum of 25%, particularly
preferably a maximum of 20%, and very particularly preferably a
maximum of 15%.
In accordance with another preferred embodiment of the present
invention, the arithmetical mean roughness Ra determined at a
molded body (plate with the dimension 60.times.60.times.2 mm)
produced from the polyamide molding compound in accordance with DIN
EN ISO 4287 (2010-07) by means of a MarSurf XR1 Surface Measuring
Station amounts to at most 0.12 .mu.m, preferably at most 0.09
.mu.m, particularly preferably from 0.01 to 0.10 .mu.m, in
particular from 0.02 to 0.09 .mu.m, and/or the surface roughness
R.sub.z amounts to at most 1.50 .mu.m, preferably at most 1.00
.mu.m, particularly preferably from 0.05 to 1.30 .mu.m, in
particular from 0.1 to 1.00 .mu.m.
In accordance with another preferred embodiment of the present
invention, the arithmetical mean roughness Ra determined at a
molded body (plate with the dimension 60.times.60.times.2 mm)
produced from the polyamide molding compound and comprising 20 wt %
glass filler (B), preferably in the form of glass fibers, in
particular in the form of E-glass fibers, in accordance with DIN EN
ISO 4287 (2010-07) by means of a MarSurf XR1 Surface Measuring
Station amounts to at most 0.1 .mu.m, preferably at most 0.07
.mu.m, particularly preferably from 0.01 to 0.08 .mu.m, in
particular from 0.02 to 0.06 .mu.m, and/or the surface roughness
R.sub.z amounts to at most 1.5 .mu.m, preferably at most 0.85
.mu.m, preferably from 0.05 to 1.0 .mu.m, in particular from 0.1 to
0.9 .mu.m.
In accordance with a further preferred embodiment of the present
invention the transparency measured in accordance with ASTM D1003
at a molded body (plate with the dimension 60.times.60.times.2 mm)
produced from the polyamide molding compound amounts to at least
80%, preferably at least 88% and the haze measured in accordance
with ASTM D1003 at a molded body (plate with the dimension
60.times.60.times.2 mm) produced from the polyamide molding
compound amounts to a maximum of 40%, preferably a maximum of 35%,
particularly preferably to a maximum of 25% and very particularly
preferably a maximum of 20%, and the arithmetical mean roughness Ra
determined at a molded body (plate with the dimension
60.times.60.times.2 mm) produced from the polyamide molding
compound and comprising 20 wt % glass filler (B), preferably in the
form of glass fibers, in particular in the form of E-glass fibers,
in accordance with DIN EN ISO 4287 (2010-07) by means of a MarSurf
XR1 Surface Measuring Station amounts to at most 0.12 .mu.m,
preferably at most 0.09 .mu.m, particularly preferably from 0.01 to
0.10 .mu.m, in particular from 0.02 to 0.09 .mu.m, and/or the
surface roughness R.sub.z amounts to at most 1.50 .mu.m, preferably
at most 1.00 .mu.m, preferably from 0.05 to 1.30 .mu.m, in
particular from 0.10 to 1.00 .mu.m
In accordance with a further preferred embodiment of the present
invention, the transparency measured at a molded body (plate with
the dimension 60.times.60.times.2 mm) produced from the polyamide
molding compound and comprising 20 wt % glass fillers (B),
preferably in the form of glass fibers, in particular in the form
of S-glass fibers, in accordance with ASTM D1003 amounts to at
least 80%, preferably at least 85%, and particularly preferably at
least 88% and the haze measured at a molded body (plate with the
dimension 60.times.60.times.2 mm) produced from the polyamide
molding compound and comprising 20 wt % glass fillers (B),
preferably in the form of glass fibers, in particular in the form
of S-glass fibers, in accordance with ASTM D1003 amounts to a
maximum of 30%, preferably to a maximum of 25%, particularly
preferably a maximum of 20%, and very particularly preferably a
maximum of 15% and the arithmetical mean roughness Ra determined at
a molded body (plate with the dimension 60.times.60.times.20 mm)
produced from the polyamide molding compound and comprising 20 wt %
glass fillers (B), preferably in the form of glass fibers, in
particular in the form of S-glass fibers in accordance with DIN EN
ISO 4287 (2010-07) by means of a MarSurf XR1 Surface Measuring
Station amounts to at most 0.1 .mu.m, preferably at most 0.07
.mu.m, particularly preferably from 0.01 to 0.08 .mu.m, in
particular from 0.02 to 0.06 .mu.m, and/or the determined surface
roughness Rz amounts to at most 1.5 .mu.m, preferably at most 0.85
.mu.m, particularly preferably from 0.05 to 1.0 .mu.m, in
particular from 0.1 to 0.9 .mu.m.
Another preferred embodiment of the invention provides that the
modulus of elasticity of the polyamide molding compound determined
in accordance with ISP 527 is in the range from 3,000 to 15,000
MPa, preferably from 5,000 to 12,000 MPa, and particularly
preferably from 5,500 to 10,000 MPa.
In accordance with another preferred embodiment of the present
invention, the failure stress of the polyamide molding compound
determined in accordance with ISO 527 amounts to greater than 80
MPa, preferably to from 100 to 250 MPa, and particularly preferably
to from 120 to 200 MPa.
In accordance with a further preferred embodiment of the present
invention, the elongation at break of the polyamide molding
compound determined in accordance with ISO 527 is greater than 2%,
preferably greater than 3%, and particularly preferably in the
range from 3 to 10%.
In accordance with another preferred embodiment of the present
invention, the impact resistance of the polyamide molding compound
determined in accordance with ISO 179/2 is preferably than 30
kJ/mm.sup.2, preferably greater than 40 kJ/mm.sup.2, and
particularly preferably from 40 to 100 kJ/mm.sup.2.
In accordance with a further preferred embodiment of the present
invention, the notch impact strength of the polyamide molding
compound determined in accordance with ISO 179/2 amounts to at
least 8 kJ/mm.sup.2, preferably to at least 9 kJ/mm.sup.2, and
particularly preferably from 10 to 20 kJ/mm.sup.2.
In accordance with a further preferred embodiment of the present
invention, the HDT A of the polyamide molding compound determined
in accordance with ISO 75 amounts to at least 120.degree. C.,
particularly preferably to at least 130.degree. C., and very
particularly preferably at least 140.degree. C., and is preferably
in the range from 120 to 200.degree. C., particularly preferably
from 130 to 180.degree. C., and very particularly preferably from
140 to 160.degree. C.
In accordance with a further preferred embodiment of the present
invention, the HDT B of the polyamide molding compound determined
in accordance with ISO 75 amounts to at least 125.degree. C.,
particularly preferably to at least 135.degree. C., and very
particularly preferably at least 145.degree. C., and is preferably
in the range from 125 to 200.degree. C., particularly preferably
from 135 to 190.degree. C., and very particularly preferably from
145 to 170.degree. C.
In accordance with another preferred embodiment of the present
invention, the polyamide molding compound is free of lactams and
aminocarboxylic acids, in particular free of aminoundecanoic acid.
It is further preferred that the polyamide molding compound is free
of polyetheramides.
A preferred polyamide molding compound in accordance with the
present invention comprises the following components and
particularly preferably consists thereof: (A) 50 to 95 wt % of a
mixture of (A1) 25 to 48% polyamide PA MACMI/MACMT/12; (A2) 52 to
75% polyamide PA MACM12; (B) 5 to 50 wt % of at least one glass
filler having a refractive index in the range from 1.510 to 1.539;
(C) 0 to 10 wt % of at least one additive.
It is in particular preferred that for this composition A1 and A2
are in the range from 0.003 to 0.03.
Furthermore, preferred polyamide molding compounds in accordance
with the present invention are those molding compounds that
comprise or consist of the following components: (A) 50 to 95 wt %
of a mixture of (A1) 25 to 48% polyamide PA MACMI/12; (A2) 52 to
75% polyamide PA MACM12; (B) 5 to 50 wt % of at least one glass
filler having a refractive index in the range from 1.510 to 1.539;
(C) 0 to 10 wt % of at least one additive, or (A) 50 to 95 wt % of
a mixture of (A1) 25 to 45% polyamide 6I/6T/612/MACMI/MACMT/MACM12;
(A2) 55 to 75% polyamide PA MACM12; (B) 5 to 50 wt % of at least
one glass filler having a refractive index in the range from 1.510
to 1.539; (C) 0 to 10 wt % of at least one additive, or (A) 50 to
95 wt % of a mixture of (A1) 25 to 45% polyamide PA MACMI/MACMT/12;
(A2) 55 to 75% polyamide PA MACM12/PACM12; (B) 5 to 50 wt % of at
least one glass filler having a refractive index in the range from
1.510 to 1.539; (C) 0 to 10 wt % of at least one additive, or (A)
50 to 95 wt % of a mixture of (A1) 25 to 45% polyamide PA
MACMI/MACMT/12; (A2) 55 to 75% polyamide PA MACM14/PACM14; (B) 5 to
50 wt % of at least one glass filler having a refractive index in
the range from 1.510 to 1.539; (C) 0 to 10 wt % of at least one
additive.
It is in particular preferred that for these compositions A1 and A2
are in the range from 0.003 to 0.03.
Molded Bodies
The present invention further relates to molded bodies comprising
the molding compound as defined above; the molded body preferably
consists of this polyamide molding compound. These molded bodies
are in particular selected from the group comprising components of
cellular telephones, tablets, housings of electronic devices, trim
parts in vehicles and at home, covers, visible surfaces, backlit
components, shields, containers, vehicle keys, and leisure and
outdoor articles.
In accordance with a preferred embodiment of the present invention,
the molded bodies are multilayer. It is in particular a two-layer
or three-layer molded body that preferably comprises only one layer
formed of the previously described molding compound in accordance
with the invention.
It is preferably a multilayer molded body formed from a layer (S1)
comprising or consisting of the polyamide molding compound in
accordance with the invention and at least one further layer (S2),
(S3), or (S4) that is free of glass fillers (B) or that has a
proportion of glass filler (B) reduced in comparison with the layer
(S1), with the glass filler proportion preferably being reduced by
at least 50 wt % with respect to the layer (S1).
These multilayer molded bodies make possible a good surface quality
even with the use of transparent polyamides of a high viscosity as
a component of the mixture (A) and/or the use of molding compounds
having a higher degree of filling of glass fillers (B) in the layer
(S1). In addition, the tool surface has a smaller influence on the
surface quality so that a good surface quality can nevertheless be
implemented even with actually suboptimal tool surfaces. This
reduces the surface roughness and the haze of the molded body and
increases its transparency, and indeed at high stiffness and
strength, which is substantially ensured by the layer (S1). Thus
these multilayer molded bodies can have a haze at a total thickness
of 2 mm of less than 10% and a transparency of more than 90%, which
demonstrates the excellent optical properties of this multilayer
system. A very resistant layer (S2), (S3), or (S4) can furthermore
provide the multilayer molded body with an overall better chemical
resistance because the possibly less resistant layer (S1) is not in
direct contact with the chemicals present. In this connection, with
a suitable choice of the outwardly disposed layers (S2) to (S4), a
multilayer molded body having good stress cracking resistance and
good chemical resistance can be obtained. The resistance toward
media and the transparency and the haze can thus be increased
without suffering large compromises in the mechanical
properties.
In accordance with another preferred embodiment, the molded body
has an arithmetical mean roughness Ra of at most 0.1 .mu.m,
preferably of 0.01 to 0.08 .mu.m, in particular of 0.02 to 0.06
.mu.m, and/or a surface roughness R.sub.z of at most 1.5 .mu.m,
preferably of 0.05 to 1.0 .mu.m, in particular from 0.1 to 0.9
.mu.m, respectively determined in accordance with DIN EN ISO 4287
(2010-07) by means of a MarSurf XR1 Surface Measuring Station.
In accordance with a further preferred embodiment of the present
invention, the transparency measured in accordance with ASTM D100
at a multilayer molded body (plate with the dimension
60.times.60.times.2 mm) produced from the polyamide molding
compound and comprising 20 wt % glass fillers (B), preferably in
the form of glass fibers, in particular in the form of E-glass
fibers, in the layer (S1) amounts to at least 80%, preferably at
least 85%, and particularly preferably at least 88% and the haze
measured in accordance with ASTM D1003 amounts to a maximum of 25%,
preferably to a maximum of 20%, particularly preferably to a
maximum of 15%, and very particularly preferably to a maximum of
12%.
Preferred layer sequences are (S1)/(S2) or (S2)/(S1)/(S2) or
(S3/(S1)/(S4). The layers are here indicated from top to bottom,
i.e. (S1)/(S2) means, for example, that (S1) forms the topmost
layer and (S2) the bottommost layer of the molded body.
In accordance with a further preferred embodiment of the present
invention, the molded body has the layers (S2), (53), or (S4) that
are based on the polyamide mixture (A), or on polyamide (A1), or on
polyamide (A2), or on a polyamide different from (A1) and (A2) and
that preferably consist thereof. The term "based/basis" in the
sense of the present application is to be interpreted such that the
layer comprises at least 50%, preferably at least 70%, and
particularly preferably at least 90%, of this layer.
Another preferred embodiment of the present invention provides that
the mean layer thickness of the layer (S1) is at least 2 times as
large, preferably at least 5 times as large, and particularly
preferably at least 9 times as large, as the sum of all the mean
layer thicknesses of the layers (S2), (S3), or (S4).
In accordance with another preferred embodiment of the present
invention, the weight ratio of the layer (S1) in the molded body is
at least 2 times larger, preferably at least 5 times larger, and
particularly preferably at least 10 times, larger, than the weight
ratio of all the layers (S2, (S3), and (S4) in the molded body.
In accordance with a further preferred embodiment of the present
invention, the layers (S2), (S3), or (S4) are on the basis of a
polyamide selected from the group comprising PA MACM12, PA
MACMI/MACMT/12, PA 6I/6T/612/MACMI/MACMT/MACM12, PA MACM12/PACM12,
PA 11, PA 12, and mixtures thereof or preferably consist
thereof.
In accordance with another embodiment of the present invention, the
layer (S2), (S3), or (S4) is back injection molded with the layer
(51) or the layers (S1) and (S2), (53), or (S4) were produced by
two-component or multi-component injection molding (mono-sandwich
process), with the multilayer molded body being integrally produced
in one injection molding cycle.
Use of Transparent Polyamide
The present invention further relates to the use of at least one
transparent polyamide (A1) that is amorphous or microcrystalline
and that has at least 25 mol % of monomers having aromatic
structural units, with respect to the total quantity of diamines
and dicarboxylic acids, for reducing the haze of a polyamide
molding compound that also has, in addition to at least one
transparent polyamide (A2) that is amorphous or microcrystalline
and has less than 25 mol % of monomers having aromatic structural
units, with respect to the total quantity of diamines and
dicarboxylic acids, a glass filler having a refractive index in the
range from 1.510 to 1.539 and optionally has additives. The
polyamides (A1) and (A2) form the polyamide mixture (A) here.
In accordance with a preferred embodiment, the proportion of the
polyamide (A1) in the polyamide mixture (A) is larger than 50 wt %
if the ratio .DELTA.2/.DELTA.1>1 and the proportion of the
polyamide (A2) in the polyamide mixture (A) comprising (A1) and
(A2) is larger than 50 wt % if the ratio
.DELTA.2/.DELTA.1.ltoreq.1.
The subject matter in accordance with the invention will be
explained in more detail with reference to the following examples
without intending to restrict it to the specific embodiments shown
here.
1 MEASUREMENT METHODS
The following measurement methods were used within the framework of
this application:
Surface Roughness, R.sub.a, R.sub.z
The roughness of the test specimens was measured in accordance with
DIN EN ISO 4287 (2010-07) using a MarSurf XR1 Surface Measuring
Station of Mahr GmbH (DE). The roughness values, that is, the
arithmetical mean roughness Ra and the surface roughtness R.sub.z,
are given in micrometers (.mu.m).
Haze, Transparency
The transparency and haze were measured in accordance with ASTM
D1003 on a measuring device Haze Gard Plus of BYK Garder at plates
of 2 mm thickness (60 mm.times.60 mm surface) with CIE light type C
at 23.degree. C. The surface of the specimen (plate
60.times.60.times.2 mm) had an arithmetical mean roughness R.sub.a
and a surface roughness R.sub.z as explicitly specified for the
molding compounds in accordance with the examples and comparison
examples in Table 2 or for the multilayer molded body. The
manufacture of the test specimens will be described under item
3.3.
Melting point (T.sub.m) and melt enthalpy (.DELTA.H.sub.m)
The melting point and the enthalpy of fusion were determined in
accordance with ISO 11357-3 (2013) on pellets. The DSC
(differential scanning calorimetry) measurements were performed at
a heating rate of 20 K/min.
Glass Transition Temperature, T.sub.g
The determination of the glass transition temperature T.sub.g took
place in accordance with ISO 11357-2 (2013) at pellets by means of
differential scanning calorimetry (DSC). It was performed in each
of the two heating steps at a heating rate of 20 K/min. The sample
was quenched in dry ice after the first heating. The glass
transition temperature (T.sub.g) was determined in the second
heating step. The center of the glass transition zone, that was
here specified as the glass transition temperature, was determined
using the "half height" method.
Relative viscosity, .eta..sub.rel The relative viscosity was
determined in accordance with IS 307 (2007) at 20.degree. C. 0.5 g
polymer pellets were weighed into 100 ml m-cresol for this purpose;
the calculation of the relative viscosity (RV) after RV=t/t.sub.0
took place on the basis of the section 11 of the standard. Modulus
of Elasticity
The determination of the modulus of elasticity was carried out in
accordance with ISO 527 (2012) at 23.degree. C. at a tensile speed
of 1 mm/min at an ISO tensile rod (type A1, mass
170.times.20/10.times.4) manufactured in accordance with the
standard: ISO/CD 3167 (2003).
Failure Stress and Elongation at Break
The determination of the failure stress and of the elongation at
break was carried out in accordance with ISO 527 (2012) at
23.degree. C. at a tensile speed of 5 mm/min at an ISO tensile rod
(type A1, mass 170.times.20/10.times.4) manufactured in accordance
with the standard ISO/CD 3167 (2003).
Impact Resistance According to Charpy
The determination of the impact resistance was carried out
according to Charpy in accordance with ISO 179/2*eU (1997,
*2=instrumented) at 23.degree. C. at an ISO test rod, Type B1 (mass
80.times.10.times.4 mm), manufactured in accordance with the
standard ISO/CD 3167 (2003).
Notch Impact Resistance According to Charpy
The determination of the notch impact resistance according to
Charpy was carried out in accordance with ISO 179/2*eA (1997,
*2=instrumented) at 23.degree. C. at an ISO test rod, Type B1 (mass
80.times.10.times.4 mm), manufactured in accordance with the
standard ISO/CD 3167 (2003).
Heat Deflection Temperature (HDT)
The heat deflection temperature (HDT) or also deformation
temperature under load is reported as HDT/A and/or HDT/B. HDT/A
corresponds to method A having a bending stress of 1.80 MPa and
HDT/B corresponds to method C having a bending stress of 0.45 MPa.
HDT was determined in accordance with ISO 75 (2013-04) at ISO
baffle rods with the dimensions 80.times.10.times.4 mm.
Measuring the Refractive Index of Glass Fibers
The determination of the refractive index of glass fibers took
place using the Beck's line method and using immersion fluids with
respect to 589 nm based on method B of ISO 489 (1999-04).
Measuring the Refractive Index of Polyamides
The refractive index of the polyamides A1 and A2 was determined in
accordance with ISO 489 (1999-04) at plates of 2 mm thickness
(60.times.60.times.2 mm) at a wavelength of 589 nm and at a
temperature of 23.degree. C. by means of an Abbe refractometer of
Carl Zeiss (method A). 1-2-bromonaphthalene was applied as the
contact fluid between the examined plate and the prism surface.
2. STARTING MATERIALS
The materials used in the examples and in the comparison examples
are collated in Table 1.
TABLE-US-00003 TABLE 1 Materials used in the examples and in the
comparison examples Components Description Manufacturer Polyamide 1
PA MACMI/MACMT/12 (38/38/24), amorphous EMS-CHEMIE AG (Component
(A1)) Rel. viscosity = 1.56 (Switzerland) Aromatic structural
units: 50 mol % Refractive index: 1.542 Transparency: 93%; Haze:
0.5%; Tg: 190.degree. C. Polyamide 2 PA MACM12 (amorphous)
EMS-CHEMIE AG (Component (A2)) Rel. viscosity = 1.71 (Switzerland)
Aromatic structural units: 0 mol % Refractive index: 1.509
Transparency: 93%; Haze: 0.3%; Tg: 155.degree. C. Polyamide 3 PA
MACM12/PACM12 (microcrystalline) EMS-CHEMIE AG (Component (A2))
Rel. viscosity = 1.82 (Switzerland) Aromatic structural units: 0
mol % Refractive index: 1.5133 Transparency: 93%; Haze: 0.4%; Tg:
145.degree. C. Melting heat: 14 J/g Polyamide 4 PA PACM12
(amorphous) EMS-CHEMIE AG (Component (A2)) Rel. viscosity = 1.86
(Switzerland) Aromatic structural units: 0 mol % Refractive index:
1.5180 Transparency: 93%; Haze: 0.7%; Tg: 141.degree. C. Glass
fiber 1 OC HPXSS HTX10 Owens Corning (BE, Refractive index = 1.516
US) Glass fiber 2 AGY SG37 553 5-32 AGY (FR) Refractive index =
1.524 LC12 Laurolactam, CAS: 947-04-6 EMS-CHEMIE AG (Switzerland)
HD-PB Exceparl hd-pb, 2-Hexyl-decyl-p- KAO Chemicals
hydroxybenzoate, CAS: 148348-12-3 Europe
3 EXAMPLES AND COMPARISON EXAMPLES
3.1 Manufacturing the Polyamide Molding Compounds
The compounds are generally mixed (compounded) on standard
compounding machines such as single-shaft or twin-shaft extruders
or screw kneaders in the polymer melt to manufacture the plastic
molding compound. The components are here individually metered into
the feeder or are supplied in the form of a dry blend. If additives
are used, they can be introduced directly or in the form of a
master batch. In a dry blend manufacture, the dried polymer pellets
and the additives are mixed. The mixing can take place under a
dried protective gas to avoid moisture absorption. The glass fibers
used are metered into the polymer melt in the intended ratio via a
side feeder and are further homogenized in the cylinder of the
compounding machine. The metering of all the components into the
feeder or side feeder are set via electronically controlled scales
such that the desired quantity ratios of glass-polymer result
therefrom.
The compounding takes place at set extruder cylinder temperatures
of e.g. 230.degree. C. to 350.degree. C. Vacuum can be applied or
atmospheric degassing can take place in front of the nozzle. The
melt is output into a water bath in extruded form and is
pelletized. An underwater pelletization or a strand pelletization
is preferably used for pelletization. The plastic molding compound
thus preferably obtained in pellet form is subsequently dried and
can then be further processed to molded bodies by injection
molding. This takes place via a repeat melting of the dry pellets
in a heatable cylinder and conveying s the melt into an injection
mold in which the melt can solidify.
3.2 Manufacture of the Polyamide Molding Compound in Accordance
with Examples B1 to B8
The molding compounds for the examples B1 to B8 and for the
comparison examples VB1 to VB3 were manufactured on a twin shaft
extruder of the company Werner and Pfleiderer, Type ZSK25. The
polyamides (A1) and (A2) were metered into the feed of the extruder
via metering trolleys in the quantity portions specified in Table
2. Fine powder LC-12 is applied to the polyamides (A1) and (A2) by
tumbling and is metered with them into the feed. HD-PB is metered
into zone 7 via a nozzle. The glass fibers used were conveyed into
the polymer melt in the intended ratio via a side feeder (zone 6)
and were further homogenized in the cylinder of the compounding
machine.
The temperature of the first housing was set to 80.degree. C.; that
of the remaining housings in an increasing manner from 270 to
300.degree. C. A speed of 200 r.p.m. and a throughput of 15 kg/h
was used and degassing took place in the third zone in front of the
nozzle in the nitrogen stream. The polyamide molding compound
output as a strand was cooled in a water bath at 80.degree. C. and
pelletized, and the obtained pellets were dried at 90.degree. C. in
vacuum at 30 mbar to a water content of below 0.1 wt %.
3.3 Manufacture of the Test Specimens
Tensile rods, baffle rods, and plates were injected from the
pellets obtained as test specimens at which the properties
specified in Table 2 were determined. The test specimens were
manufactured on an injection molding machine of Arburg, model
Allrounder 420 C 1000-250. Increasing cylinder temperatures from
250.degree. C. to 290.degree. C. were used here. The melt
temperature for all the injected molded bodies amounted to
290-300.degree. C. in each case. The tool temperature was at
120.degree. C. in each case in the case of plates (2 mm.times.60
mm.times.60 mm). The tool temperatures of the tensile rods and of
the baffle rods were 80.degree. C. in each case. The test specimens
were used in the dry state if not otherwise specified; for this
purpose, they were stored at room temperature for at least 48 h
after the injection molding in a dry environment, i.e. over silica
gel.
In the case of plates (2 mm.times.60 mm.times.60 mm) for
determining the optical properties, the surfaces of the cavity of
the injection mold were given a mirror finish so that the molded
bodies (plates) had a high gloss surface having an arithmetical
mean roughness Ra of 0.01 to 0.08 .mu.m and/or a surface roughness
Rz of 0.05 to 1.0 .mu.m, in accordance with DIN EN ISO 4287.
3.4 Results
3.4.1 Single-Layer Molded Bodies
The following Table 2 relates to examples in accordance with the
present invention, and comparison examples.
TABLE-US-00004 TABLE 2 Examples and comparison examples. Unit B1 B2
B3 B4 B5 B6 Components Polyamide 1 Wt % 36 40.5 31.5 28 10 24
Proportion of (A1) in (A) Wt % 45.0 45.0 45.0 35.0 12.5 30.0
Polyamide 2 Wt % 44 49.5 38.5 -- -- -- Polyamide 3 Wt % -- -- -- 52
70 -- Polyamide 4 Wt % -- -- -- -- -- 56 Proportion of (A2) in (A)
Wt % 55.0 55.0 55.0 65.0 87.5 70.0 .DELTA.1 -- 0.018 0.018 0.018
0.018 0.026 0.018 .DELTA.2 -- 0.015 0.015 0.015 0.0107 0.0027 0.006
.DELTA.2/.DELTA.1 -- 0.83 0.83 0.83 0.59 0.10 0.33 HD-PB Wt % -- --
-- -- -- -- LC12 Wt % -- -- -- -- -- -- Glass fiber 1 Wt % -- -- --
-- 20 -- Glass fiber 2 Wt % 20 10 30 20 -- 20 Properties Tg molding
compound .degree. C. 148 148 148 148 154 151 Haze molding compound
% 18 10 28 20 22 21 Transparency % 90 92 89 90 90 90 Molding
compound Tg Mixture A .degree. C. 148 148 148 148 154 152 Haze
Mixture A % 0.5 0.5 0.5 0.7 0.7 0.8 Transparency Mixture A % 93 93
93 93 93 92 Ra plate 60 .times. 60 .times. 2 mm .mu.m 0.059 0.050
0.063 0.061 0.059 0.062 Rz plate 60 .times. 60 .times. 2 mm .mu.m
0.784 0.688 0.833 0.797 0.761 0.812 Modulus of elasticity MPa 6130
3480 8180 5900 6100 5800 Tensile strength MPa 148 89 170 135 132
133 Elongation at break % 4.1 7.7 3.4 4.8 5.6 4.4 Impact resistance
kJ/mm.sup.2 48 34 54 92 94 70 Notch impact resistance kJ/mm.sup.2
12 10 12 12 13 11 HDT A .degree. C. 157 154 158 151 152 143 HDT B
.degree. C. 164 163 165 156 156 146 B7 B8 VB1 VB2 VB3 VB4
Components Polyamide 1 33.75 22.9 56 50 80 -- Proportion of (A1) in
(A) 45.0 28.6 70 62.5 100 -- Polyamide 2 41.25 57.1 24 30 -- 80
Polyamide 3 -- -- -- -- -- -- Polyamide 4 -- -- -- -- -- --
Proportion of (A2) in (A) 55.0 71.4 30.0 37.5 -- 100 .DELTA.1 0.018
0.026 0.026 0.018 -- -- .DELTA.2 0.015 0.007 0.007 0.015 -- --
.DELTA.2/.DELTA.1 0.83 0.27 0.27 0.83 -- -- HD-PB 5 -- -- -- -- --
LC12 -- 5 -- -- -- -- Glass fiber 1 -- 15 20 -- -- 20 Glass fiber 2
20 -- -- 20 20 -- Properties Tg molding compound 148 154 160 158
190 155 Haze molding compound 19 16 43 48 79 86 Transparency 90 90
87 88 84 86 Molding compound Tg Mixture A 148 154 161 158 -- --
Haze Mixture A 0.7 0.5 1.7 0.5 -- -- Transparency Mixture A 92 93
93 93 -- -- Ra plate 60 .times. 60 .times. 2 mm 0.055 0.058 0.059
0.057 0.055 0.058 Rz plate 60 .times. 60 .times. 2 mm 0.746 0.722
0.779 0.764 0.750 0.717 Modulus of elasticity 6020 5260 5790 6250
5880 5750 Tensile strength 149 132 128 131 133 129 Elongation at
break 3.3 3.3 4.4 4.4 4.0 6.1 Impact resistance 33 35 47 46 45 88
Notch impact resistance 10 10 11 11 10 12 HDT A -- -- 161 158 175
135 HDT B -- -- 168 165 180 141
3.4.2 3-Layer Molded Bodies of the Dimension 60.times.60.times.2 mm
Manufacture of the Multilayer Molded Bodies
The following multilayer molded bodies of the dimension
60.times.60.times.2 mm were manufactured by back injection molding
of films of non-reinforced, transparent polyamide using the
polyamide molding compound in accordance with the invention. The
manufacture took place on an injection molding machine of Arburg
420C 1000-250 using the conditions described above for the
60.times.60.times.2 mm plates. Two extruded films produced from the
polyamide 1 (PA MACMI/MACMT/12 (component (A1)), each having a
thickness of 100 mm were cut to the size 60.times.60.times.0.1 mm,
were placed into the injection molding tool, and the remaining
cavity between the two films after the closing of the tool was
filled by injection the polyamide molding compound in accordance
with the invention from example 1 or 3. After cooling, the
multilayer molded body was demolded and the transparency and haze
were determined in accordance with ASTM D1003. The insertion films
of polyamide 1 were no longer able to be removed from the
multilayer molded body after the injection molding process, but
were rather connected with material continuity to the molding
compound from the examples B1, B4, and B7.
TABLE-US-00005 Multilayer molded body 1 Film of polyamide 1 (t)
Structure of the multilayer External Molding compound molded body
of the dimension Central of example 1 60 .times. 60 .times. 2 mm
Internal Film of polyamide 1 (b) Transparency % 91 Haze % 7.0 Ra
(t/b) (plate 60 .times. 60 .times. 2 mm) .mu.m 0.021/0.022 Rz (t/b)
(plate 60 .times. 60 .times. 2 mm) .mu.m 0.248/0.252 Multilayer
molded body 2 Film of polyamide 1 (t) Structure of the multilayer
External Molding compound molded body of the dimension Central of
example 4 60 .times. 60 .times. 2 mm Internal Film of polyamide 1
(b) Transparency % 91 Haze % 6.5 Ra (t/b) (plate 60 .times. 60
.times. 2 mm) .mu.m 0.022/0.025 Rz (t/b) (plate 60 .times. 60
.times. 2 mm) .mu.m 0.255/0.314 Multilayer molded body 3 Film of
polyamide 1 (t) Structure of the multilayer External Molding
compound molded body of the dimension Central of example 7 60
.times. 60 .times. 2 mm Internal Film of polyamide 1 (b)
Transparency % 91 Haze % 6.3 Ra (t/b) (plate 60 .times. 60 .times.
2 mm) .mu.m 0.023/0.026 Rz (t/b) (plate 60 .times. 60 .times. 2 mm)
.mu.m 0.244/0.326
4 DISCUSSION OF THE RESULTS
It can be seen from Table 2 that the polyamide molding compounds in
accordance examples B1 to B8 in accordance with the invention have
very good optical properties. The haze of the filled polyamide
molding compounds is in the range from 16 to 28% and the
transparency is in the range from 89 to 92%. The polyamide molding
compounds in accordance with the comparison examples VB1 to VB4 in
contrast demonstrate much higher haze values in the range from 43
to 86%. The polyamide molding compounds in accordance with the
comparison examples VB3 and VB4 each comprise only one polyamide
(A1) or (A2), whereas the polyamide molding compounds in accordance
with the comparison examples VB1 and VB2 just like the polyamide
molding compounds in accordance with the invention comprise a
mixture of the polyamides (A1) and (A2). The polyamide molding
compounds in accordance with the comparison examples VB1 and VB2,
however, satisfy the condition that the content of (A2) in the
mixture (A) is >50 wt % if the ratio is not
.DELTA.2/.DELTA.1.ltoreq.1, but the proportion of (A1) in mixture
(A) is greater than 50 wt % in these polyamide molding compounds.
Providing polyamide molding compounds filled with a glass filler
that have very good optical properties is therefore surprisingly
only successful by the specific feature combination in accordance
with the invention. Since the surface roughness in all examples is
at the same high level, the differences in transparency and in haze
clearly originate from the selected composition of the molding
compound.
It has further been shown that multilayer molded bodies that have
very good optical properties, in particular a low haze and good
transparency can also be manufactured from the polyamide molding
compounds in accordance with the invention. These molded bodies
furthermore have a very good surface, the mean roughness value Ra
and the surface roughness R.sub.z are in particular at a low level
and this is despite the use of high viscosity starting materials
(A1) and (A2). Due to the high viscosity of the starting
substances, on the other hand, the high strength and toughness of
the molded bodies is ensured; the impact resistance and the
elongation at break are in particular considerably improved with
respect to low viscosity types.
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